CN106513032A - Molecular sieve catalyst for preparation of polyoxymethylene dimethyl ethers - Google Patents
Molecular sieve catalyst for preparation of polyoxymethylene dimethyl ethers Download PDFInfo
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- CN106513032A CN106513032A CN201610944599.3A CN201610944599A CN106513032A CN 106513032 A CN106513032 A CN 106513032A CN 201610944599 A CN201610944599 A CN 201610944599A CN 106513032 A CN106513032 A CN 106513032A
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- molecular sieve
- catalyst
- zsm
- acid
- dimethyl ether
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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
-
- 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
- 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
-
- 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
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a molecule sieve catalyst for preparation of polyoxymethylene dimethyl ethers. The method includes: subjecting a ZSM-5 molecular sieve to acid solution treatment, and carrying out washing, drying and roasting treatment to obtain a modified HZSM-5 molecular sieve catalyst. The invention adopts modified ZSM-5 as the catalyst, which does not have the problems of homogeneous catalysts and loaded catalysts, also is free of the active center loss problem of ion exchange resin. At the same time, compared with existing HZSM-5 catalyst, the catalyst provided by the invention greatly reduces the by-product selectivity and increases the yield of DMMn.
Description
Technical field
The present invention relates to a kind of molecular sieve catalyst for preparing polymethoxy dimethyl ether, belongs to methanol derived energy chemical technology neck
Domain.
Background technology
Polymethoxy dimethyl ether (Polyoxymethylene dimethyl ethers, abbreviation PODE or DMMn) it is one
The low-molecular-weight acetal polymer with methylene epoxide as main chain is planted, its structural formula is CH3(OCH2)nOCH3。
Synthesis DMMnRaw material and catalyst performance determine the Technical Economy of whole technique, wherein catalyst is which again
In key.Catalyst performance is mainly reflected in catalyst and activity and selectivity, has high DMMnThe selectivity of series product and
Low by-product（Methanol, formic acid and methyl formate etc.）Selectivity.
Synthesis DMMnCatalyst be mainly acidic catalyst, including mineral acid, organic acid, solid acid, load oxide
With ionic liquid etc..
U.S.'s Southwest Research Institute patents US5746785 are with dimethoxym ethane and paraformaldehyde as original
Material, adopts 0.1% formic acid for catalyst, reacts to synthesize DMM at 150～240 DEG C1-10。
Acidic catalyst is adopted in BASF Aktiengellschaft patent application CN101048357, US2007260094（Such as
Mineral acid, sulfonic acid, heteropoly acid, acid-exchange resin, zeolite, aluminosilicate, silicon dioxide, aluminium oxide, titanium dioxide and
Zirconium dioxide）, with DMM and TOX as Material synthesis DMM3-4, it is desirable to the water yield being introduced in reactant mixture is mixed less than based on reaction
The 0.2% of compound meter, then by distilling DMM of the acquisition comprising wherein n=3 and 4nFraction, and DMM, TOX and wherein n ＜ 3
And the optionally DMM of n ＞ 4nIt is re-circulated into reaction.In limited reactions thing, water content is because that PODE hydrolysis generates hemiacetal（It is single
Ether）And low polymerization degree paraformaldehyde, its boiling point and DMMnQuite, separate difficult.In its patent application CN101198576A with two
Alkyl ether and TOX are raw material, and other conditions are identical with CN101048357.
BP Amoco companies adopt DME and DME silver catalyst oxidative dehydrogenations（US5959156）Or Cu-Zn-Se catalytic dehydrogenations
（US6160186）The formaldehyde of generation is in MFI molecular sieve catalysts（SiO2/Al2O3The ZSM-5 or borosilicate MFI molecular sieves of ＞ 10）Urge
Change and prepare DMMn.Product includes water, methanol, formaldehyde, DME and DMM1-10.Rectification product obtains the tower bottom liquid without DME（First
Alcohol, formaldehyde and DMM）Jing solid acid catalysts（Cation exchange resin, bentonite and sulfonated tertafluorethylene resin etc.）Prepare
DMMn.It is also adopted by being come by the formaldehyde and DME of the preparation of molybdenum oxide catalyst catalysis oxidation methanol in the said firm's patent US6166266
Synthesis DMMn, or US6265528 patents adopt methanol and by DME silver catalytic oxidative dehydrogenation generate formaldehyde in catalytic distillation tower
Reaction prepares DMMn, it is characterized in the solid acid catalyst activated using condensation accelerator formic acid or acetic acid（Cation exchange tree
Fat and sulfonated tetrafluorethylene resin）.
With methanol and TOX as raw material in Lanzhou Physical and Chemical Inst. of Chinese Academy of Sciences patent application CN101182367A,
With the ionic liquid selected from glyoxaline cation, pyridylium etc. and the composition such as toluene sulfonic acide root, trifluoro sulfonate radical as catalysis
Agent is synthesizing DMMn.And the cation of the ionic liquid adopted in its patent application CN102040545A is for tetraalkyl guanidine, patent
Then using dumbbell shape cationes such as bi-quaternary ammonium salt class, double imidazoles in application CN101962318A.Chinese Academy of Sciences Lanzhou is physico
With DMM and TOX as raw material in institute patent CN101665414B, adopt functionalization acidic ionic liquid body for catalyst to make
Standby DMMn, wherein ionic liquid is selected from 1- methyl -3- (4- sulfonic group butyl) glyoxaline cations or 1- methyl -3- (4- butyl sulphurs
Sour methyl ester) glyoxaline cation, anion is selected from bisulfate ion or pyrovinic acid root.
" a kind of synthesis is poly- for Beijing Dongfang Hongsheng New Energy Application Technology Institute Co., Ltd. application 103664550 A of CN
The method of methoxy methyl acetal ", it is 100～120 DEG C to invent initial temperature of the technique by controlling to react, and passes through successive
Stepwise or programmed cooling control reaction pressure for 0.1～4.0MPa, the paraformaldehyde or metaformaldehyde to 50～70 DEG C
Raw material is counted with the mol ratio of the dimethoxym ethane as 1.5 with formaldehyde molal quantity:1～8:1 realizes.The technique is when identical is reacted
The interior purpose product total recovery that can be reached is higher, and the selectivity of high methoxyl degree of polymerization product increases.Adopted
Catalyst be storng-acid cation exchange resin.
Sinopec Group CN103420812A with methanol or DME with formaldehyde or TOX as raw material, to have
The molecular sieve for having RUT topological structure synthesizes DMM for catalystn, DMM in product3-8Up to 32.2%.Its patent application
CN103664546A adopts ZSM-5 molecular sieve of the particle diameter less than 3 μm for catalyst, wherein SiO in the raw material of synthesis ZSM-52/
Al2O3For 200:1.Then with methanol, DMM and TOX as raw material in CN102040488B, using β zeolites, ZSM-5, MCM-22 or
At least one molecular sieve in MCM-56 is catalyst.
As mineral acid or organic acid are homogeneous catalyst, which is difficult to separate thorough, causes product acid to spend height, and easily
Equipment corrosion is caused, there are various problems in actual applications.Although and ionic-liquid catalyst have preferably activity and
DMM3-8Selectivity, but it there is also catalyst high cost, the problem difficult to equipment corrosion, separation and recovery of catalyst；Meanwhile,
Ionic liquid typically contains sulfonate radical, causes product sulfur-bearing, reduces product quality（DMM3-8Mainly as diesel fuel additives, must
The relevant criterion of diesel oil, such as acidity and moisture must be met）.
In order to solve the problems such as homogeneous catalyst (organic acid, mineral acid and ionic liquid etc.) is difficult to be separated, being first will be equal
Phase catalyst carries out immobilized, such as load-type ion liquid and suported superacid.But due to the moisture that formaldehyde is brought into, cause load
Type catalyst loss, activity decrease.
Another selection is to adopt solid acid catalyst, such as ion exchange resin and molecular sieve catalyst etc..The former is answering
Subject matter with is that catalyst active center has certain loss, the such as loss of sulfonate radical so that product sulfur-bearing, be increased
Acidity, it is necessary to carry out deacidification and desulfurization process.And molecular sieve catalyst is mainly MFI, MCM-22, β zeolite etc..But due to molecule
Sieve acidity and its complexity of distribution, and for the complexity of formaldehyde polyaddition reaction, it is not right in existing patent application
Zeolite molecular sieve catalyst is in synthesis DMMnIn make concrete detailed requirement, such as SiO2/Al2O3（US5959156 or
US6160186 requires ZSM-5 or borosilicate MFI molecular sieve SiO2/Al2O3＞ 10）, or molecular sieve particle diameter（CN103664546A is adopted
The ZSM-5 molecular sieve that 3 μm of particle diameter ＜ is catalyst）.
In addition, in above-mentioned patent or patent application, major concern target product, and the not by-product selectivity with regard to catalyst
It is analyzed.By-product selectivity increases, except reducing DMMnSelectivity outside, also increase product separating difficulty and product acid
Degree.Ordinary diesel oil standard GB 252-2015 requires acidity≤7 mgKOH/100mL.Separation process is DMM againnIn building-up process
One of key problem, be to realize DMMnOne of industrialized major obstacle.Therefore synthesize DMMnCatalyst except with high
DMM3-8Selectivity, is preferably provided with low by-product selectivity and low acidity.
The content of the invention
It is an object of the invention to it is to solve current DMM to overcomenThe problem that synthetic catalyst is present, there is provided prepared by one kind
The molecular sieve catalyst of polymethoxy dimethyl ether.The present invention proposes to adopt modified HZSM-5 for catalyst, and it is both without homogeneous
The problem of catalyst and loaded catalyst, also no ion exchange resin active center losing issue, while comparing existing
HZSM-5 catalyst, significantly reduces the selectivity of by-product, improves DMMnYield.
For achieving the above object, the technical solution used in the present invention is as follows：
A kind of molecular sieve catalyst for preparing polymethoxy dimethyl ether, it is characterised in that：By ZSM-5 molecular sieve at acid solution
After reason, washing, drying and calcination process, Modified HZSM-5 Zeolite Catalyst is obtained.
The ZSM-5 molecular sieve includes NaZSM-5, NH4- ZSM-5 or HZSM-5 molecular sieves.
During the acid solution is processed, ZSM-5 molecular sieve powder or ZSM-5 preformed catalysts are carried out at acidic aqueous solution
Reason, treatment temperature are 50～150 DEG C, and process time is 0.5～24h.
In the washing, filtered after acid solution process, then deionized water is washed to neutrality.
In the drying, the ZSM-5 catalyst after washing is dried, temperature 90～140, the time is 1～5h.
In the calcination process, dried ZSM-5 catalyst is carried out into high-temperature process, treatment temperature is 150～600
DEG C, roasting time is 0.5～8h.
The acid solution processes acid used for one kind of oxalic acid, citric acid, tartaric acid or nitric acid or in any proportion
It is several.
The acid solutions are 0.1～15, and the mass ratio of acid solution and molecular sieve is 2～50:1.
The roasting condition is air atmosphere, N2Under atmosphere or roasting under vacuum, preferred atmosphere is N2Or vacuum.
Using it is an advantage of the current invention that：
First, the modified HZSM-5 catalyst after the present invention is processed is in synthesis DMMnIn, have than the ZSM-5 catalyst of before processing
There is more preferable target product DMMnSelectivity and relatively low by-product selectivity, wherein by-product is formic acid and methyl formate
Deng.
2nd, the Modified HZSM-5 Zeolite Catalyst prepared by the present invention is used to synthesize DMMn, and the raw material of synthesis includes first
It is water-soluble that alcohol, dimethoxym ethane, metaformaldehyde, paraformaldehyde or formalin, wherein formalin are preferably high-concentration formaldehyde
Liquid.
3rd, modified HZSM-5 molecular sieve is in synthesis DMMnIn, its active center is its acid centre.Comprising extremely in molecular sieve
Few two kinds of acid centres：Lewis acid and Br nsted are sour.By modification, in modulation molecular sieve acid site type and its
Distribution, hence it is evident that change the catalysis activity and selectivity of molecular sieve：Not only DMM in product2-8Concentration improves 94.23～
148.66%, DMM3-8Concentration improves 2.58 times to 4.52 times, and Main By product methyl formate then reduce 20.60～
39.04%（It is shown in Table 1）, and objectionable impurities methyl formate content is minimum can reduce by 83.85%, and the content of acidity (formic acid) is most
It is low to reduce by 32.24～59.95%（It is shown in Table 2）.
Specific embodiment
Embodiment 1
By 10gHZSM-5（SiO2/Al2O3=60）Molecular sieve powder is placed in the aqueous citric acid solution 100g that concentration is 10%, is stirred
80 DEG C are warming up under the conditions of mixing, process 6h after filtered, wash to filtrate for neutrality, then in an oven 100 DEG C be dried 3h.
500 DEG C of roasting 2h in Muffle furnace are finally placed in, HZSM-5 modified catalyst HZSM-5-C1 are obtained.
Embodiment 2
By 10gHZSM-5（SiO2/Al2O3=60）Molecular sieve powder is placed in the aqueous citric acid solution 100g that concentration is 10%, is stirred
80 DEG C are warming up under the conditions of mixing, process 4h after filtered, wash to filtrate for neutrality, then in an oven 110 DEG C be dried 3h.
The lower 500 DEG C of roasting 2h of vacuum in tube furnace are finally placed in, HZSM-5 modified catalyst HZSM-5-C2 are obtained.
Embodiment 3
2.1g catalyst, 30.0g metaformaldehydes and 76.1g dimethoxym ethanes are placed in 150mL reactors, high-purity N2After displacement 6 times
0.60MPa is boosted to, 100 DEG C is then heated to and is reacted.Less than 10 DEG C are cooled to after reaction 30min, using 0.2 μm poly- four
Fluoride film carries out filter pressing, and separating catalyst obtains product.Taking product carries out chromatography, determines target product and main by-product
Thing methyl formate content, determines product acidity.Evaluating catalyst result such as table 1 prepared by unmodified catalyst and embodiment 1 and 2
It is shown.It can be seen that, modified through the present invention, selectivity of catalyst is greatly improved, and acidity is also largely dropped
It is low.
Table 1 is modified and unmodified HZSM-5 evaluating catalysts result
Embodiment 4
By 10gHZSM-5（SiO2/Al2O3=100）Molecular sieve powder is placed in the aqueous citric acid solution 100g that concentration is 10%, is stirred
80 DEG C are warming up under the conditions of mixing, process 6h after filtered, wash to filtrate for neutrality, then in an oven 100 DEG C be dried 3h.
550 DEG C of roasting 2h in Muffle furnace are finally placed in, HZSM-5 modified catalyst HZSM-5-C3 are obtained.
Embodiment 5
10gHZSM-5 molecular sieve powders are placed in the oxalic acid aqueous solution 100g that concentration is 10%, under stirring condition, 80 is warming up to
DEG C, process 6h after filtered, wash to filtrate for neutrality, then in an oven 100 DEG C be dried 3h.Finally it is placed in Muffle furnace
550 DEG C of roasting 2h, obtain HZSM-5 modified catalyst HZSM-5-C4.
Embodiment 6
Evaluating catalyst and analysis method are with embodiment 3.HZSM-5（SiO2/Al2O3=100）Unmodified catalyst and embodiment 4
It is as shown in table 2 with the 5 evaluating catalyst results for preparing.It can be seen that, modified through the present invention, selectivity of catalyst is obtained greatly
Improve, acidity is also greatly reduced.
Table 2 is modified and unmodified HZSM-5 evaluating catalysts result
Embodiment 7
ZSM-5 molecular sieve is processed, washs, is done through acid solution by a kind of molecular sieve catalyst for preparing polymethoxy dimethyl ether
After dry and calcination process, Modified HZSM-5 Zeolite Catalyst is obtained.
The ZSM-5 molecular sieve includes NaZSM-5, NH4- ZSM-5 or HZSM-5 molecular sieves.
During the acid solution is processed, ZSM-5 molecular sieve powder or ZSM-5 preformed catalysts are carried out at acidic aqueous solution
Reason, treatment temperature are 50～150 DEG C, and process time is 0.5～24h.
In the washing, filtered after acid solution process, then deionized water is washed to neutrality.
In the drying, the ZSM-5 catalyst after washing is dried, temperature 90～140, the time is 1～5h.
In the calcination process, dried ZSM-5 catalyst is carried out into high-temperature process, treatment temperature is 150～600
DEG C, roasting time is 0.5～8h.
The acid solution processes acid used for one kind of oxalic acid, citric acid, tartaric acid or nitric acid or in any proportion
It is several.
The acid solutions are 0.1～15, and the mass ratio of acid solution and molecular sieve is 2～50:1.
The roasting condition is air atmosphere, N2Under atmosphere or roasting under vacuum, preferred atmosphere is N2Or vacuum.
Claims (9)
1. a kind of molecular sieve catalyst for preparing polymethoxy dimethyl ether, it is characterised in that：By ZSM-5 molecular sieve through acid solution
After process, washing, drying and calcination process, Modified HZSM-5 Zeolite Catalyst is obtained.
2. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 1, it is characterised in that：The ZSM-
5 molecular sieves include NaZSM-5, NH4- ZSM-5 or HZSM-5 molecular sieves.
3. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 1 and 2, it is characterised in that：It is described
In acid solution process, ZSM-5 molecular sieve powder or ZSM-5 preformed catalysts are carried out into acidic aqueous solution process, treatment temperature
For 50～150 DEG C, process time is 0.5～24h.
4. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 3, it is characterised in that：The washing
In, filtered after acid solution process, then deionized water is washed to neutrality.
5. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 1,2 or 4, it is characterised in that：Institute
State in being dried, the ZSM-5 catalyst after washing is dried, temperature 90～140, the time is 1～5h.
6. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 5, it is characterised in that：The roasting
In process, dried ZSM-5 catalyst being carried out into high-temperature process, treatment temperature is 150～600 DEG C, roasting time is 0.5～
8h。
7. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 1,2,4 or 6, it is characterised in that：
It is several that the acid solution processes acid used for one kind of oxalic acid, citric acid, tartaric acid or nitric acid or in any proportion.
8. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 7, it is characterised in that：The acid is molten
Liquid concentration is 0.1～15, and the mass ratio of acid solution and molecular sieve is 2～50:1.
9. the molecular sieve catalyst for preparing polymethoxy dimethyl ether according to claim 1,2,4,6 or 8, its feature exist
In：The roasting condition is air atmosphere, N2Under atmosphere or roasting under vacuum, preferred atmosphere is N2Or vacuum.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108212197A (en) * | 2018-01-23 | 2018-06-29 | 西南化工研究设计院有限公司 | A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application |
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|---|---|---|---|---|
| CN102211036A (en) * | 2010-04-09 | 2011-10-12 | 上海吴泾化工有限公司 | Modified molecular sieve catalyst, and precursor and preparation method thereof |
| CN103121927A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxymethylal |
| CN104725229A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院大连化学物理研究所 | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate |
| US20150231607A1 (en) * | 2012-03-30 | 2015-08-20 | Basf Corporation | Catalyst for tetrahydrofuran synthesis |
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2016
- 2016-11-02 CN CN201610944599.3A patent/CN106513032A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102211036A (en) * | 2010-04-09 | 2011-10-12 | 上海吴泾化工有限公司 | Modified molecular sieve catalyst, and precursor and preparation method thereof |
| CN103121927A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxymethylal |
| US20150231607A1 (en) * | 2012-03-30 | 2015-08-20 | Basf Corporation | Catalyst for tetrahydrofuran synthesis |
| CN104725229A (en) * | 2013-12-23 | 2015-06-24 | 中国科学院大连化学物理研究所 | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108212197A (en) * | 2018-01-23 | 2018-06-29 | 西南化工研究设计院有限公司 | A kind of dimethyl ether is for the catalyst of polymethoxy dimethyl ether and its preparation and application |
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Application publication date: 20170322 |