CN109647516B - Catalyst for preparing polyformaldehyde dimethyl ether - Google Patents
Catalyst for preparing polyformaldehyde dimethyl ether Download PDFInfo
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- CN109647516B CN109647516B CN201710937995.8A CN201710937995A CN109647516B CN 109647516 B CN109647516 B CN 109647516B CN 201710937995 A CN201710937995 A CN 201710937995A CN 109647516 B CN109647516 B CN 109647516B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title abstract description 50
- 229920006324 polyoxymethylene Polymers 0.000 title abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 24
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical group C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 39
- 239000003729 cation exchange resin Substances 0.000 claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- 239000004793 Polystyrene Substances 0.000 claims description 36
- -1 polyoxymethylene dimethyl ether Polymers 0.000 claims description 36
- 229920002223 polystyrene Polymers 0.000 claims description 36
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- 150000004692 metal hydroxides Chemical class 0.000 claims 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 abstract description 27
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 21
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 39
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- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
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- 229960000583 acetic acid Drugs 0.000 description 9
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- 238000003860 storage Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 239000007900 aqueous suspension Substances 0.000 description 7
- 238000004817 gas chromatography Methods 0.000 description 7
- 239000012362 glacial acetic acid Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000003957 anion exchange resin Substances 0.000 description 6
- 150000001735 carboxylic acids Chemical class 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
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- 229910052748 manganese Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910052713 technetium Inorganic materials 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical class [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 239000002808 molecular sieve Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000011973 solid acid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000003930 superacid Substances 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
-
- 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
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for preparing polyformaldehyde dimethyl ether, which solves the problem of low product yield of a process for synthesizing the polyformaldehyde dimethyl ether by using methylal and paraformaldehyde as raw materials.
Description
Technical Field
The invention relates to a catalyst for preparing polyoxymethylene dimethyl ether.
Background
The resource pattern of China has the characteristics of rich coal, less oil and gas, and the vigorous industrial development of China puts increasing requirements on petroleum supply. However, in recent years, petroleum resources in China are increasingly tense, and the pressure of petroleum supply is increasing unprecedentedly. According to statistics, the foreign dependence of China in 2011 reaches 56.5%, and the petroleum is increased by 1.7% compared with 2010. Since the country is first to be the pure import country of petroleum in 1993, the external dependence of petroleum in China is increased by 6% of the year, and the 2009 breaks through 50% of the warning line. How to solve the energy crisis of China by using abundant coal resources of China becomes a problem which needs to be solved urgently by researchers. Therefore, people pay more attention to the development of novel fuel oil substitutes from coal base.
In addition, due to the dual pressure of air pollution and energy shortage, energy conservation and emission reduction become a subject of social development. Thus, the petrochemical industry has long been working on developing new emission-reduced diesel fuels. Many emerging alternative diesel fuels have been developed, including: GTL diesel, biodiesel, ethanol diesel, dimethyl ether, diesel oil oxygen-containing compounds, emulsified diesel oil and the like. Most of them are produced by synthetic method without using petroleum, basically do not contain impurities of sulfur, nitrogen and aromatic hydrocarbon, and are very clean diesel oil or diesel oil blending components, which are highly valued in recent years, and all countries are making great effort to develop and popularize. Among them, the use of diesel blending components does not require additional devices or changes in engine structure, and thus is considered to be a convenient and effective measure.
Dimethyl ether is firstly proposed as an additive of diesel oil, and the addition of a proper amount of dimethyl ether into the diesel oil can effectively reduce particulate matters and CO in tail gasxAnd NOxAnd (4) discharging. However, dimethyl ether has some defects due to its physical properties, such as poor cold start performance, high vapor pressure at normal temperature, easy generation of vapor lock, storage, transportation, low-pressure liquefaction and other high costs, which obviously increase the cost of dimethyl ether as an alternative fuel for vehicles. Polyoxymethylene dimethyl ethers (PODE) is a generic term for a class of substances, and can be represented by the general formula CH3O(CH2O)nCH3Having a higher cetane number (>40) And oxygen content (42-51%). When the value of n is 1, the polyformaldehyde dimethyl ether is methylal, and the methylal serving as the vehicle fuel additive component can improve the energy utilization efficiency and reduce the exhaust emission, but is still easy to cause air lock. When the value of n is 2-6, the physical property and the combustion performance of the diesel oil are very close to those of diesel oil, and the defects of dimethyl ether and methylal serving as blending components of the diesel oil for vehicles are overcome. Therefore, the polyoxymethylene dimethyl ether can be used as a novel clean diesel component, the addition amount in the diesel can reach more than 10 percent (v/v), the combustion condition of the diesel in an engine can be improved, the thermal efficiency is improved, and particulate matters and CO in tail gas are reducedxAnd NOxAnd (4) discharging. The optimal chain length of the polyoxymethylene dimethyl ether mixed with the diesel oil is n-3, 4. When n is 2, the flash point of polyoxymethylene dimethyl ether is too low, and when n is too large, polyoxymethylene dimethyl ether may precipitate and clog at a low temperature. Reportedly, 5-30% CH is added3OCH2OCH3Can greatly reduce NOxAnd (5) discharging.
The middle of PODE is paraformaldehyde segment, and two ends are sealed by methyl. PODE is generally synthesized from a compound which provides paraformaldehyde (formaldehyde, trioxane, paraformaldehyde, etc.) and a compound which provides a blocked methyl group (methanol, dimethyl ether, methylal, etc.). PODE can be synthesized by acid-catalyzed dehydration of methylal and formaldehyde or paraformaldehyde and trioxymethylene. The synthesis of synthesis gas from coal gasification, synthesis of methanol from synthesis gas, and synthesis of methylal, and the synthesis of formaldehyde from methanol by oxidation, and the preparation of paraformaldehyde or trioxymethylene from formaldehyde have been already industrialized. The PODE synthesized by the coal-based methanol can replace part of diesel oil, improve the combustion efficiency of the diesel oil, reduce the harm of the combustion of the diesel oil to the environment, and has important strategic significance and good economic value. The development and synthesis of PODE can convert rich coal resources in China into liquid alternative fuels, reduce the import dependence of China on petroleum and further have great significance to national energy safety.
Polyoxymethylene dimethyl ethers in laboratories can be prepared by heating paraformaldehyde with low polymerization degree or reacting paraformaldehyde with methanol at 150-180 ℃ in the presence of trace amounts of sulfuric acid or hydrochloric acid. Since polyoxymethylene dimethyl ethers have great application values in the field of diesel additives, a large number of companies and research institutes have been researching feasible industrial production technologies for a long time.
EP2228359A1 describes a process for preparing polyoxymethylene dimethyl ethers from methanol as starting material. The method uses a molecular sieve modified by ammonium molybdate and ferric nitrate as a catalyst, and methanol and air (oxygen) are oxidized in one step at the temperature of more than 200 ℃ to obtain the polyoxymethylene dimethyl ether. The method has relatively low production cost, but the preparation process of the catalyst is complex, and the selectivity of the polyoxymethylene dimethyl ether is not ideal.
EP1070755 describes a process for preparing polyoxymethylene dimethyl ethers having 2 to 6 formaldehyde units per molecule by reacting methylal with paraformaldehyde in the presence of trifluorosulfonic acid. WO2006/045506A1 describes that BASF company obtains a series of products with n being 1-10 by using sulfuric acid and trifluoromethanesulfonic acid as catalysts and methylal, paraformaldehyde and trioxymethylene as raw materials. The above methods all adopt protonic acid as a catalyst, which is cheap and easy to obtain, but has the defects of strong corrosivity, difficult separation, large environmental pollution and high requirement on equipment.
US6160174 and US6265528 describe that the BP company obtains polyoxymethylene dimethyl ether by a gas-solid reaction using methanol, formaldehyde, dimethyl ether and methylal as raw materials and cation exchange resin as a catalyst. However, this method has the advantages of easy separation of catalyst, easy circulation, low conversion rate, low yield and complex process.
The CN 101768057A takes methanol and trioxymethylene as raw materials and takes solid superacid as a catalyst to catalyze and synthesize polyformaldehyde dimethyl ether, although a good raw material conversion rate is obtained, due to the strong acidity of the solid superacid and the irregular pore structure, the selectivity of a byproduct methylal in a product is 20-50%, the flash point of a diesel oil mixture is reduced due to the large amount of methylal, the quality of the diesel oil mixture is damaged, and the product is not suitable for being used as an additive of diesel oil. CN 101048357A introduces a synthesis process for synthesizing polyoxymethylene dimethyl ethers by taking methylal and trioxymethylene as raw materials. We also developed a solid acid catalyst (molecular sieve CN 200910056820.1, solid super acid CN 200910056819.9) to prepare polyoxymethylene dimethyl ether from methanol and trioxymethylene.
However, the processes all adopt trioxymethylene as a reaction raw material, and the price of the trioxymethylene is 14000 yuan/ton according to market research; compared with the price of paraformaldehyde, the price of the paraformaldehyde is only 5000 yuan/ton. We have found that the production cost of polyoxymethylene dimethyl ether from paraformaldehyde can be greatly reduced.
CN 101182367A discloses a process method for synthesizing polyformaldehyde dimethyl ether by using acid ionic liquid as a catalyst and formaldehyde as synthetic trioxymethylene and then using trioxymethylene and methanol. Although the method has high one-way yield, the used ionic liquid catalyst is expensive and difficult to separate, and the operation difficulty is higher. US5,959,156 describes a process for the synthesis of polyoxymethylene dimethyl ethers starting from dimethyl ether and methanol using a novel heterogeneous promoted condensation catalyst. Although the process is low in cost, the product yield is not ideal.
Disclosure of Invention
The invention aims to solve the technical problem that the product yield of the process for synthesizing the polyoxymethylene dimethyl ethers by using methylal and paraformaldehyde as raw materials in the prior art is low, and provides a novel catalyst for preparing the polyoxymethylene dimethyl ethers. The catalyst has the advantage of high product selectivity of n-2-10.
The second technical problem to be solved by the present invention is to provide a method for preparing the catalyst by using the first technical problem.
The third technical problem to be solved by the present invention is the application of the catalyst described in one of the above technical problems.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows:
the catalyst for preparing the polyoxymethylene dimethyl ether is cation exchange resin modified by metal ions, and the metal comprises IB group metal. The IB group metal modified sulfonic acid type polystyrene cation exchange resin obviously improves the selectivity of PODE (peroxidase) with n being 2-10.
In the above technical solution, the group IB element is preferably at least one selected from Cu and Ag; more preferably Cu.
In the above-mentioned technical solution, the content of the modified metal in the catalyst is not particularly limited, but is not limited to, for example, the content of the modified metal in the catalyst is more than 0 and 9.8 w% or less.
In the technical scheme, the total exchange capacity of the resin is 3.0-5.9 mmol/g.
In the above technical solution, the resin may be of a gel type or a macroporous type.
In the above technical solution, the resin is preferably sulfonic acid type polystyrene cation exchange resin.
In the above technical scheme, the sulfonic acid type polystyrene comprises a crosslinked polystyrene skeleton and a sulfonic acid group.
In the above technical solution, the metal preferably includes VIIB metal.
In the technical scheme, the VIIB metal is preferably selected from at least one of Mn and Tc, Cu and Mn, and Cu and Tc have synergistic effect in improving selectivity of PODE (podE) with n being 2-10. The ratio between Cu and Mn, and Cu and Tc is not particularly limited, for example but not limited to, independently selected from mass ratios of 0.01 to 100, further non-limiting examples within this range are 0.1, 0.5, 0.8, 1, 1.5, 2, 3,4, 5,6, 7, 8, 9, 10, and the like.
In the technical scheme, the VIIB metal more preferably comprises Mn and Tc, and the Mn and the Tc have a synergistic effect on improving the selectivity of PODE (podE) with n being 2-10. The ratio between Mn and Tc is not particularly limited, and is selected from, for example, but not limited to, a mass ratio of 0.01 to 100, and further non-limiting examples within this range are 0.1, 0.5, 0.8, 1, 1.5, 2, 3,4, 5,6, 7, 8, 9, 10, and the like.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
the method for preparing a catalyst according to any one of the above technical problems, comprising contacting the cation exchange resin with a suspension containing the modified metal oxide and/or hydroxide in the presence of a catalytic amount of an acid to effect ion exchange.
In the above technical scheme, the acid is not particularly limited as long as the salt obtained by the reaction with the modified metal oxide and/or hydroxide can be dissolved in the solvent used for the suspension, and in this principle, for example, but not limited to, at least one of hydrochloric acid, nitric acid, and C2 to C10 carboxylic acids.
In the above technical scheme, the carboxylic acid may be a hydroxy-substituted carboxylic acid, such as but not limited to glycolic acid, lactic acid, tartaric acid, citric acid, and the like.
In the above technical scheme, the carboxylic acid may be a C2-C10 monobasic acid, such as but not limited to acetic acid and the like.
To solve the third technical problem, the technical scheme of the invention is as follows:
use of a catalyst according to any one of the preceding technical problems for the synthesis of polyoxymethylene dimethyl ethers.
The technical key of the invention is the selection of the catalyst, and for a specific application method, the technical personnel in the field can reasonably select the catalyst without creative labor.
For example, the specific application method may be:
a process for synthesizing polyoxymethylene dimethyl ether from methylal and paraformaldehyde includes such steps as heating paraformaldehyde in mixing tank to become formaldehyde gas, nitrogen flushing, drying in drying tube, bubbling in reactor, under the action of a solid acid catalyst, the mixture which is recycled and introduced into a reaction kettle reacts with methylal to generate polyformaldehyde dimethyl ether, a separation zone comprises an anion exchange resin bed layer, a rectification module and a product storage tank, the process step of the separation zone is that the discharged material of a reactor enters the rectification module after being deacidified by the anion exchange resin bed layer, the discharged material of the reactor enters the product storage tank after being separated by the rectification module, the tri-polymer and the tetramer of the polyformaldehyde dimethyl ether enter the product storage tank, and other components circulate to the reactor.
In the technical scheme, the mass ratio of methylal to paraformaldehyde is preferably 0.02-50: 1. The reaction temperature is preferably 50-250 ℃; the reaction pressure is 0.01-20.0 MPa. The reaction residence time is preferably 0.5-10.0 h. The temperature of the mixing tank is preferably 200 to 300 ℃, and more preferably 240 to 280 ℃. Recovering a first fraction comprising methylal, a second fraction comprising dimers of methanol polyoxymethylene dimethyl ether, and a fourth fraction comprising polyoxymethylene dimethyl ether of higher degree of polymerization (n >4) that are passed into the reactor mixture, preferably separated by a rectification module; preferably, the rectification module also separates a third fraction containing the tri-and tetramers of polyoxymethylene dimethyl ether. The rectification module preferably consists of 3 rectification columns. The first fraction is preferably taken off at the top of the first rectification column, the second fraction is preferably taken off at the top of the second rectification column, the third fraction is preferably taken off at the top of the third rectification column and the fourth fraction is preferably taken off at the bottom of the third rectification column. The first, second and fourth fractions are preferably recycled to the reaction system after being dewatered by a dehydrator. The operating pressure of the first rectifying tower is preferably 0.2-2 MPa, the operating pressure of the second rectifying tower is preferably 0.02-1.2 MPa, and the operating pressure of the third rectifying tower is preferably 0.001-0.6 MPa. The theoretical plate number of the first rectifying tower is preferably 15-25, the theoretical plate number of the second rectifying tower is preferably 15-30, and the theoretical plate number of the third rectifying tower is preferably 15-35.
In the above technical solution, the solid acid catalyst is selected from the metal-modified cation exchange resins.
In order to solve the second technical problem, the technical scheme of the invention is as follows:
in the above technical solution, the preparation method of the catalyst comprises contacting the sulfonic acid type polystyrene cation exchange resin with a suspension containing the modified metal oxide and/or hydroxide in the presence of a catalytic amount of acid to perform ion exchange.
In the above technical scheme, the acid is not particularly limited as long as the salt obtained by the reaction with the modified metal oxide and/or hydroxide can be dissolved in the solvent used for the suspension, and in this principle, for example, but not limited to, at least one of hydrochloric acid, nitric acid, and C2 to C10 carboxylic acids.
In the above technical scheme, the carboxylic acid may be a hydroxy-substituted carboxylic acid, such as but not limited to glycolic acid, lactic acid, tartaric acid, citric acid, and the like.
In the above technical scheme, the carboxylic acid may be a C2-C10 monobasic acid, such as but not limited to acetic acid and the like.
In the above technical solution, the drying agent used in the drying tube and the dehydrator is preferably selected from at least one of the following drying agents: ion exchange resin, molecular sieve and silica gel.
In the above technical scheme, the rectifying tower is preferably a packed tower, and the packing is preferably stainless steel or ceramic with a regular structure.
The invention has the following advantages: firstly, the yield and the selectivity are high, and the sum of n-3 and n-4 products is high in the sum of n-2-5 products; secondly, the production cost is low; thirdly, recycling the by-products by adopting a rectification method; and a better technical effect is achieved.
Drawings
The invention will be described in further detail with reference to fig. 1. FIG. 1 is a process flow diagram of the present invention.
The method comprises the following steps that nitrogen (material flow 2) output by a nitrogen storage tank 1 sweeps paraformaldehyde (material flow 3) to a mixing tank 4, the mixing tank 4 is connected with a heater 5, the paraformaldehyde is heated to be gas in the mixing tank 4, the output material flow 6 (mixed gas of nitrogen, formaldehyde gas and water vapor) is dried through a drying pipe 7 to remove water vapor to obtain a material 8, the material 8 is fed to a bubbling reactor 9, meanwhile, a material flow 14 (liquid-phase methylal) output by a methylal storage tank 13 is fed to the reactor 9, a material 19 (the main component is methylal) with water removed is recovered from the top of a rectifying tower 15, and a material 24 (the main component is a di-polymer, a pentamer and a hexamer of methanol and polyoxymethylene dimethyl ether) with water removed by a water remover 23. The reactor discharge 10 is deacidified by an anion exchange resin bed layer 12 to obtain a material 11, and the material 11 enters a rectifying tower 15 for separation. Unreacted methylal is discharged from the top of the rectifying tower 15 (material flow 17), and discharged 19 is introduced into the bubbling reactor 9 again after being dewatered by a dehydrator 18. The bottom 16 of the rectifying tower 15 is discharged to enter a rectifying tower 20 for next separation. Unreacted methanol and the generated polyoxymethylene dimethyl ether dimer are discharged from the top of the rectifying tower 20 (material flow 22), and are introduced into the bubbling reactor 9 again after being dehydrated by a dehydrator 23. The bottom discharge 21 of the rectifying tower 20 enters a rectifying tower 25 for further separation. The trimer and tetramer of polyoxymethylene dimethyl ether are discharged from the top of the rectifying tower 25 (stream 27) and enter a product storage tank 28. Polyoxymethylene dimethyl ether with higher polymerization degree (n is more than 4) is discharged from the bottom of the rectifying tower 25 (material flow 26), is dehydrated by a dehydrator 23 and then is introduced into the bubbling reactor 9 again. The nitrogen brought into the device during feeding is condensed by a condenser at the top of the rectifying tower 15 and then discharged from a non-condensable gas outlet of the condenser (not shown in the figure).
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking up the resin equivalent to the dry base resin 98 g of sulfonic acid polystyrene cation exchange resin and 300ml of Cu (OH) containing 2 g of Cu2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
In the reaction process shown in the attached figure, the reactor 9 has a volume of 2L, and is provided with an electric stirring device and an electric heating sleeve for heating.
150g of catalyst is filled in the bubbling reactor 9, a nitrogen purging device is used, 10000g of paraformaldehyde is continuously added into a mixing tank, the temperature of the mixing tank is 250 ℃, and the formaldehyde gas generated after heating is dehydrated by a drying pipe and then enters the bubbling reactor 9; at the same time, methylal was fed into the bubbling reactor 9, and the recovered mixture (methanol, formaldehyde and PODEn ═ 1,2,5,6) was circulated, wherein the feed rates of the starting materials methylal and formaldehyde were 76g/h and 90g/h, respectively. The operating conditions of the bubble reactor 9 were a reaction temperature of 110 ℃ and a reaction pressure of 2.0 MPa. The reaction discharge enters an anion exchange resin bed layer.
The reactor discharge 10 enters a rectifying tower 15 for separation after being deacidified by an anion exchange resin bed layer 12, the operating pressure is 1.10MPa, and the theoretical plate number is 20. Unreacted methylal is discharged from the top of the rectifying tower 15 (stream 17), and is subjected to water removal by a water remover 18 and then is introduced into the bubbling reactor 9 again. The bottom material discharged from the rectifying tower 15 enters a rectifying tower 20 for next separation, the operating pressure is 0.56MPa, and the theoretical plate number is 20. Unreacted methanol and the generated polyoxymethylene dimethyl ether dimer are discharged from the top of the rectifying tower 20 (material flow 22), and are introduced into the bubbling reactor 9 again after being dehydrated by a dehydrator 23. The bottom discharge 21 of the rectifying tower 20 enters a rectifying tower 25 for next separation, the operating pressure is 0.30MPa, and the theoretical plate number is 20. The trimer and tetramer of polyoxymethylene dimethyl ether are discharged from the top of the rectifying tower 25 (stream 27) and enter a product storage tank 28. Polyoxymethylene dimethyl ether with higher polymerization degree (n is more than 4) is discharged from the bottom of the rectifying tower 25 (material flow 26), is dehydrated by a dehydrator 23 and then is introduced into the bubbling reactor 9 again. The reaction was continued for 80h and the product was sampled on-line and analyzed by gas chromatography and the results are given in Table 1.
[ example 2 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Mn (OH) 2 g of Mn under nitrogen protection2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Mn content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are shown in Table 1.
[ example 3 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of Tc (OH) containing 2 g of Tc under nitrogen2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Tc content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are shown in Table 1.
[ example 4 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Mn under the protection of nitrogen2And Mn (OH)2Mixing the mixed aqueous suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w% and the Mn content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are shown in Table 1.
[ example 5 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin was mixed with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Tc under nitrogen2And Tc (OH)2Mixing the mixed aqueous suspensions, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the Cu-containing materialCatalyst in an amount of 1 w% and a Tc content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are shown in Table 1.
[ example 6 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Cu (OH) containing 1 g of Cu, 0.5 g of Tc and 0.5 g of Mn under nitrogen protection2、Tc(OH)2And Mn (OH)2Mixing the mixed aqueous suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1 w%, the Tc content of 0.5 w% and the Mn content of 0.5 w%.
2. Synthesis of polyformaldehyde dimethyl ether
150g of catalyst is filled in the bubbling reactor 9, a nitrogen purging device is used, 10000g of paraformaldehyde is continuously added into a mixing tank, the temperature of the mixing tank is 250 ℃, and the formaldehyde gas generated after heating is dehydrated by a drying pipe and then enters the bubbling reactor 9; at the same time, methylal was fed into the bubbling reactor 9, and the recovered mixture (methanol, formaldehyde and PODEn ═ 1,2,5,6) was circulated, wherein the feed rates of the starting materials methylal and formaldehyde were 76g/h and 90g/h, respectively. The operating conditions of the bubble reactor 9 were a reaction temperature of 110 ℃ and a reaction pressure of 2.0 MPa. The reaction discharge enters an anion exchange resin bed layer.
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are shown in Table 1.
[ example 7 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Cu (OH) containing 1.5 g of Cu, 0.25 g of Tc and 0.25 g of Mn under nitrogen protection2、Tc(OH)2And Mn (OH)2Mixing the mixed aqueous suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Cu content of 1.5 w%, the Tc content of 0.25 w% and the Mn content of 0.25 w%.
2. Synthesis of polyformaldehyde dimethyl ether
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are shown in Table 1.
TABLE 1
n is polymerization degree, and the product is CH3O(CH2O)nCH3。
Claims (9)
1. The catalyst for preparing the polyoxymethylene dimethyl ether is cation exchange resin modified by metal ions, the metal comprises Cu and VIIB metal, and the VIIB metal is Mn.
2. The catalyst of claim 1 wherein the amount of modifying metal in the catalyst is greater than 0 and not greater than 9.8% by weight.
3. The catalyst according to claim 1, wherein the resin has a total exchange capacity of 3.0 to 5.9 mmol/g.
4. The catalyst according to claim 1, wherein the resin is of the gel type or macroporous type.
5. The catalyst according to claim 1, wherein the resin is a polystyrene cation exchange resin of sulfonic acid type.
6. The catalyst as set forth in claim 5, characterized in that said sulfonic acid type polystyrene cation exchange resin comprises a crosslinked polystyrene skeleton and sulfonic acid groups.
7. A process for preparing a catalyst as claimed in any one of claims 1 to 6, which comprises ion-exchanging the cation exchange resin by contacting it with a suspension containing the modified metal oxide and/or the modified metal hydroxide in the presence of a catalytic amount of an acid.
8. The method according to claim 7, wherein the acid is at least one of hydrochloric acid, nitric acid and C2-C10 carboxylic acid.
9. Use of the catalyst of any one of claims 1 to 6 in the synthesis of polyoxymethylene dimethyl ethers.
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| CN104549443B (en) * | 2013-10-28 | 2017-04-19 | 中国石油化工股份有限公司 | polyformaldehyde dimethyl ether catalyst and application thereof |
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| CN106582834A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparation of polyoxymethylene dimethyl ether |
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