CN107930699A - A kind of preparation method of metaformaldehyde acetalation catalyst - Google Patents

A kind of preparation method of metaformaldehyde acetalation catalyst Download PDF

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CN107930699A
CN107930699A CN201711300856.0A CN201711300856A CN107930699A CN 107930699 A CN107930699 A CN 107930699A CN 201711300856 A CN201711300856 A CN 201711300856A CN 107930699 A CN107930699 A CN 107930699A
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preparation
metaformaldehyde
catalyst
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water
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张永伟
韩济泽
王刚
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Jiangsu Normal University
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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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/165—Polymer immobilised coordination complexes, e.g. organometallic complexes
    • B01J31/1658—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
    • B01J31/1683—Polymer immobilised coordination complexes, e.g. organometallic complexes immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins the linkage being to a soluble polymer, e.g. PEG or dendrimer, i.e. molecular weight enlarged complexes
    • 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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/035—Precipitation on carriers
    • 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
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • 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
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • C07D323/04—Six-membered rings
    • C07D323/06—Trioxane
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16—Copper

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Abstract

The invention discloses a kind of preparation method of metaformaldehyde acetalation catalyst, Cu（NO3）·3H20th, 199 nano materials of MOF, 1,4,5,8 naphthalenetetracarbacidic acidics, soluble starch and ammonium chloride are primary raw material, by 1,4, the hydrolysate of 5,8 naphthalenetetracarbacidic acidics and water soluble starch as organic ligand, and make its with after the complexation reaction of copper source, so as to generate the space symmetr structure of cubic lattice, similar Cu is avoided the occurrence of3（BTC）2Web wheel-like structure, the starch conversion hybridized metal organic catalyst of invention is used for metaformaldehyde acetalation, and technique is simple, and cost of material is low, has higher activity and selectivity to synthesis polymethoxy dimethyl ether.

Description

A kind of preparation method of metaformaldehyde acetalation catalyst
Technical field
The present invention relates to a kind of metaformaldehyde acetalation catalyst and preparation method thereof, belong to catalyst technical field.
Background technology
Polymethoxy dimethyl ether (polyoaymethylene dimethyl ether CH30(CH2O)-CH3, DMMnOr PODEn)
It is a kind of more ether compounds, works as DMMnMolecule Central Asia methoxyl group n<It is at normal temperatures water white transparency, volatile when 3 Liquid, has chloroform smell, can be dissolved in the water for being three times in its volume, easily dissolve each other with alcohols and ethers.Work as n>When 5, at normal temperatures White solid.DMMnWith very high Cetane number (CN values, DMM2:63, DMM3:78, DMM4:90, DMM5: 100) (oxygen content 42-49%, flash-point are 64-84 DEG C, meet diesel oil safety standard, boiling point is between 156-268 DEG C, just with oxygen content Benefit is in diesel range.Therefore, DMMnIt is considered as a kind of excellent environment-friendly type diesel oil blending component.In recent years, with coal The development of chemical industry, ripe as the technology of Material synthesis methanol using coal, the production capacity of domestic methanol is in the situation of rapid growth, by It is inadequate in Downstream Products, cause methanol excess capacity, therefore promote exploitation Downstream Products of Methanol and develop to high added value Sound development for coal chemical industry has far reaching significance.
The content of the invention
It is an object of the invention to provide a kind of preparation method of metaformaldehyde acetalation catalyst, the catalyst energy Catalytic trimerization formaldehyde acetalization is reacted under cryogenic, has higher activity and stability.
A kind of preparation method of metaformaldehyde acetalation catalyst, this method comprise the following steps：
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, 3g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；
Step 2, be placed on above-mentioned mixed liquor is closed in ultrasonic oscillator, and adjusting ultrasonic frequency is 100KHz, ultrasonic wave Power is 450W, and ultrasonic vibration is to there is sky blue sediment at room temperature；
Step 3 and then 1. 08g of soluble starch aqueous solution that mass concentration is 25wt% is added dropwise, maintains ultrasound condition not Become, continue ultrasound 35min.Obtained mixed solution suction filtration is handled, obtains filter cake；
Above-mentioned filter cake, be put into the aqueous acetone solution containing ammonium chloride by step 4, and the mass ratio of filter cake and ammonium chloride is 2:1, chlorine Change, the ratio of ammonium and acetone is 1g:The volume ratio of 120mL, acetone and water is 1:2, rotating speed is mechanical agitation 60min under 70rpm, Mixed liquor suction filtration is handled, multiple to distill water washing, to much filtrate drying process, dry 180min, obtains starch at 215 DEG C Modified hybridized metal organic catalyst.
The MOF-199 preparation method of nano material is as follows：
Step 1, weigh 250 mg 1,3,5- equal benzoic acid are added to the n,N-Dimethylformamide and second of 40 m L In the mixed solution of alcohol（Volume ratio is 3: 1）, while by 430mg copper acetates C4H6CuO4·H2O is dissolved in 20ml water, is obtained Mixed liquor；
Step 2, by above-mentioned mixed liquor be stirring evenly and then adding into 0.25ml triethanolamines, after mixed solution is stirred 3h, by product Filtering, is washed 5 times with deionized water and DMF respectively, is dried, is obtained metal-organic framework materials MOF-199.
Beneficial effect：It is anti-to be used for metaformaldehyde acetalation the present invention provides a kind of starch conversion hybridized metal organic catalyst Should, by Isosorbide-5-Nitrae, the hydrolysate of 5,8- naphthalenetetracarbacidic acidics and water soluble starch makes itself and the complexation reaction of copper source as organic ligand Afterwards, so as to generate the space symmetr structure of cubic lattice, similar Cu is avoided the occurrence of3（BTC）2Web wheel-like structure.And starch or water Solution into more carbon glucose units there is the network of side chain, can further metal-organic framework materials network be repaiied Decorations, generation more complicatedization, the pore passage structure more to narrow, so as to just more improve the effect of absorption of the catalyst to reactant molecule Rate so that metaformaldehyde conversion ratio greatly improves, and preparation process is simple, and cost of material is low, anti-to metaformaldehyde acetalation There should be higher activity and selectivity.
Embodiment
Embodiment 1
A kind of preparation method of metaformaldehyde acetalation catalyst, this method comprise the following steps：
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, 3g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；
Step 2, be placed on above-mentioned mixed liquor is closed in ultrasonic oscillator, and adjusting ultrasonic frequency is 100KHz, ultrasonic wave Power is 450W, and ultrasonic vibration is to there is sky blue sediment at room temperature；
Step 3 and then 1. 08g of soluble starch aqueous solution that mass concentration is 25wt% is added dropwise, maintains ultrasound condition not Become, continue ultrasound 35min.Obtained mixed solution suction filtration is handled, obtains filter cake；
Above-mentioned filter cake, be put into the aqueous acetone solution containing ammonium chloride by step 4, and the mass ratio of filter cake and ammonium chloride is 2:1, chlorine Change, the ratio of ammonium and acetone is 1g:The volume ratio of 120mL, acetone and water is 1:2, rotating speed is mechanical agitation 60min under 70rpm, Mixed liquor suction filtration is handled, multiple to distill water washing, to much filtrate drying process, dry 180min, obtains starch at 215 DEG C Modified hybridized metal organic catalyst.
The MOF-199 preparation method of nano material is as follows：
Step 1, weigh 250 mg 1,3,5- equal benzoic acid are added to the n,N-Dimethylformamide and second of 40 m L In the mixed solution of alcohol（Volume ratio is 3: 1）, while by 430mg copper acetates C4H6CuO4·H2O is dissolved in 20ml water, is obtained Mixed liquor；
Step 2, by above-mentioned mixed liquor be stirring evenly and then adding into 0.25ml triethanolamines, after mixed solution is stirred 3h, by product Filtering, is washed 5 times with deionized water and DMF respectively, is dried, is obtained metal-organic framework materials MOF-199.
Embodiment 2
Step 1, weigh 3gCu（NO3）·3H20th, 9g MOF-199 nano materials, 3g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Embodiment 3
Step 1, weigh 6gCu（NO3）·3H20th, 3g MOF-199 nano materials, 3g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Embodiment 4
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, 12g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Embodiment 5
Step 1, weigh 12gCu（NO3）·3H20th, 18g MOF-199 nano materials, 3g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Embodiment 6
Step 1, weigh 6gCu（NO3）·3H20th, 36g MOF-199 nano materials, 3g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Embodiment 7
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, 18g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Embodiment 8
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, 21g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Embodiment 9
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, 6 parts of cross-linked rectorites/SAPO-34 composite woods Material, 3g Isosorbide-5-Nitraes, 5,8- naphthalenetetracarbacidic acidics are added in 2000g aqueous acetone solutions, and the volume ratio of acetone and water is 1:2, it is uniformly mixed Afterwards, 0.01molL is added-1Hydrochloric acid solution adjust mixed liquor pH=0.5；Remaining step is the same as embodiment 1.
The preparation method of the cross-linked rectorite/SAPO-34 composite materials is as follows：
After 15 parts of SAPO-34 and 5 part of cross-linked rectorites are dried, crushing is ground, 600 mesh sieve, and are mixed at 90 DEG C Uniformly, it is dispersed in one deionized water solution of ethanol, adds 14 parts of cetyl trimethylammonium bromides in 60 DEG C of stirred in water bath 4 Hour, ultrasonic disperse 30 minutes, filters, and washing, is dried under vacuum to constant weight, grinds, and sieves up to cross-linked rectorite/SAPO-34 Composite material.
Embodiment 10
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, 3g 1,4,5,8 naphthalenetetracarboxylic acids are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；Remaining step is the same as embodiment 1.
Reference examples 1
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, MOF-199 nano materials are not added, remaining step It is identical with embodiment 1.
Reference examples 2
It is with 1 difference of embodiment：In the step 1 of catalyst preparation, substitute aqueous acetone solution with ethanol water, remaining step Suddenly it is identical with embodiment 1.
Reference examples 3
It is with 1 difference of embodiment：In the step 3 of catalyst preparation, amidin is not added, remaining step is with implementing Example 1 is identical.
Reference examples 4
It is with 1 difference of embodiment：In the step 3 of catalyst preparation, be added dropwise mass concentration be 25wt% sucrose it is water-soluble 1. 08g of liquid, remaining step are identical with embodiment 1.
Reference examples 5
It is with 1 difference of embodiment：In the step 4 of catalyst preparation, ammonium chloride is not added, remaining step and embodiment 1 It is identical.
Reference examples 6
It is with 1 difference of embodiment：In the step 4 of catalyst preparation, above-mentioned filter cake is put into the acetone water containing common salt In solution, the mass ratio of filter cake and ammonium chloride is 2:1, remaining step is identical with embodiment 1.
Reference examples 7
It is with 1 difference of embodiment：In MOF-199 nano materials preparation process 1, the 1 of 50 mg are weighed, 3,5- equal benzene Formic acid, remaining step are identical with embodiment 1.
Reference examples 8
It is with 1 difference of embodiment：In MOF-199 nano materials preparation process 1, the 1 of 300 mg are weighed, 3,5- is equal Benzoic acid, remaining step are identical with embodiment 1.
Reference examples 9
It is with 1 difference of embodiment：In MOF-199 nano materials preparation process 1, n,N-Dimethylformamide and ethanol it is mixed It is 1: 1 with liquor capacity ratio, remaining step is identical with embodiment 1.
Reference examples 10
It is with 1 difference of embodiment：In MOF-199 nano materials preparation process 1, n,N-Dimethylformamide and ethanol it is mixed It is 3: 1 with liquor capacity ratio, remaining step is identical with embodiment 1.
The catalyst that embodiment and reference examples are prepared is used for metaformaldehyde acetalation, and polymethoxy dimethyl ether exists Carried out in the stainless steel cauldron of 110ml, reactant molar ratio CH3OH：TOX=1.2:1, loaded catalyst is the total matter of raw material Amount 3wt%, 150 DEG C, pressure 0.5MPa of temperature, when stirring reaction 8 is small, post catalyst reaction and liquid product supercentrifuge Separation, the product liquid obtained after centrifugation Shimadzu GC2014C type chromatographics；
It is as shown in the table for reaction result.
Test result indicates that catalyst has metaformaldehyde acetalation good catalytic effect, it is certain in reaction condition When, polymethoxy dimethyl ether（DMM3-10）Selectivity is higher, and catalytic performance is better, otherwise poorer；In Cu（NO3）·3H20、MOF- 199 nano materials, 1,4,5,8 naphthalenetetracarboxylic acid quality are 2:6:When 1, other dispensings are fixed, and catalytic effect is best, with embodiment 1 Difference is that embodiment 2 to embodiment 10 changes catalyst primary raw material Cu respectively（NO3）·3H20th, MOF-199 nanometers of materials Material, Isosorbide-5-Nitrae, the dosage and proportioning of 5,8- naphthalenetetracarbacidic acidics, have different influences to the catalytic performance of catalyst, it should be noted that real Apply example 9 and add cross-linked rectorite/SAPO-34 composite materials, polymethoxy dimethyl ether selectively significantly improves, and illustrates that crosslinking is tired Support stone/SAPO-34 composite materials have more preferable optimization function to the structure-activity of catalyst；Reference examples 1 are to reference examples 2 with not Add MOF-199 nano materials and substitute acetone with ethanol, other steps are identical, cause the activity of catalyst to become Change, polymethoxy dimethyl ether selectivity is obvious to be reduced；Reference examples 3 to reference examples 4 replace water soluble starch with sucrose so that modified Agent changes, and catalytic activity reduces, and positive effect is deteriorated；Reference examples 5 substitute ammonium chloride with sodium chloride to reference examples 6 and change Proportioning, effect is still bad, illustrates the compound critically important of ammonium chloride；Reference examples 7 to reference examples 10 change the equal benzene first of 1,3,5- Acid, the materials of n,N-Dimethylformamide and ethanol match, and the structure of MOF-199 nano materials changes, catalytic effect according to It is so bad；Therefore the catalyst prepared using the present invention has excellent catalytic effect to metaformaldehyde acetalation.

Claims (3)

1. a kind of preparation method of metaformaldehyde acetalation catalyst, it is characterised in that this method comprises the following steps：
Step 1, weigh 6gCu（NO3）·3H20th, 18g MOF-199 nano materials, the 1,4,5,8 naphthalenetetracarboxylic acid of 3g are added to In 2000g aqueous acetone solutions, the volume ratio of acetone and water is 1:2, after mixing, add 0.01molL-1Hydrochloric acid solution Adjust pH=0.5 of mixed liquor；
Step 2, be placed on above-mentioned mixed liquor is closed in ultrasonic oscillator, and adjusting ultrasonic frequency is 100KHz, ultrasonic wave Power is 450W, and ultrasonic vibration is to there is sky blue sediment at room temperature；
Step 3 and then the soluble starch aqueous solution 1.08g that mass concentration is 25wt% is added dropwise, maintains ultrasound condition not Become, continue ultrasound 35min；
Obtained mixed solution suction filtration is handled, obtains filter cake；
Above-mentioned filter cake, be put into the aqueous acetone solution containing ammonium chloride by step 4, and the mass ratio of filter cake and ammonium chloride is 2:1, chlorine Change, the ratio of ammonium and acetone is 1g:The volume ratio of 120mL, acetone and water is 1:2, rotating speed is mechanical agitation 60min under 70rpm, Mixed liquor suction filtration is handled, multiple to distill water washing, to much filtrate drying process, dry 180min, obtains starch at 215 DEG C Modified hybridized metal organic catalyst.
A kind of 2. preparation method of metaformaldehyde acetalation catalyst according to claim 1, it is characterised in that
The MOF-199 preparation method of nano material is as follows：
Step 1, weigh 250 mg 1,3,5- equal benzoic acid are added to the n,N-Dimethylformamide and ethanol of 40 m L Mixed solution in, while by 430mg copper acetates C4H6CuO4·H2O is dissolved in 20ml water, obtains mixed liquor；
Step 2, by above-mentioned mixed liquor be stirring evenly and then adding into 0.25ml triethanolamines, after mixed solution is stirred 3h, by product Filtering, is washed 5 times with deionized water and DMF respectively, is dried, is obtained metal-organic framework materials MOF-199.
3. a kind of preparation method of metaformaldehyde acetalation catalyst according to claim 2, it is characterised in that described N,N-Dimethylformamide and ethanol volume ratio be 3: 1.
CN201711300856.0A 2017-12-10 2017-12-10 A kind of preparation method of metaformaldehyde acetalation catalyst Pending CN107930699A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106495996A (en) * 2016-10-21 2017-03-15 中国石油大学(北京) A kind of method with lewis acid as catalyst preparation polymethoxy dimethyl ether
CN106622143A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Hybridized organic framework material and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106622143A (en) * 2015-11-03 2017-05-10 中国石油化工股份有限公司 Hybridized organic framework material and preparation method and application thereof
CN106495996A (en) * 2016-10-21 2017-03-15 中国石油大学(北京) A kind of method with lewis acid as catalyst preparation polymethoxy dimethyl ether

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李菲菲等: "金属有机骨架材料MOF-199的制备及其吸附性能研究", 《辽宁化工》 *

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