CN102350371A - Mesoporous molecular sieve catalyst and application of catalyst in synthesis of ethylene glycol monobutyl ether - Google Patents
Mesoporous molecular sieve catalyst and application of catalyst in synthesis of ethylene glycol monobutyl ether Download PDFInfo
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- CN102350371A CN102350371A CN2011102297216A CN201110229721A CN102350371A CN 102350371 A CN102350371 A CN 102350371A CN 2011102297216 A CN2011102297216 A CN 2011102297216A CN 201110229721 A CN201110229721 A CN 201110229721A CN 102350371 A CN102350371 A CN 102350371A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000015572 biosynthetic process Effects 0.000 title claims abstract 3
- 238000003786 synthesis reaction Methods 0.000 title claims abstract 3
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims abstract 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- 238000001125 extrusion Methods 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- 238000000465 moulding Methods 0.000 description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- 230000002194 synthesizing effect Effects 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 238000007493 shaping process Methods 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 241000282326 Felis catus Species 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229960003511 macrogol Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical class CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种介孔分子筛催化剂及其在乙二醇单丁醚合成中的应用，其中的催化剂的制备方法是以Al-MCM-41介孔分子筛催化剂为原粉，以γ-氧化铝作为粘合剂，以硝酸、多元羧酸和聚乙二醇6000为助剂，通过挤条方法使催化剂成型。本发明的催化剂具有强度好、耐压强的性能，在间歇搅拌釜反应器中搅拌5小时仍能保持颗粒状态，无明显破碎现象。本发明催化剂具有良好的催化活性，并且可以重复利用，乙二醇单丁醚收率达36%。
The present invention discloses a mesoporous molecular sieve catalyst and its application in the synthesis of ethylene glycol monobutyl ether. As a binder, nitric acid, polycarboxylic acid and polyethylene glycol 6000 are used as auxiliary agents, and the catalyst is molded by extrusion method. The catalyst of the invention has the performance of good strength and strong pressure resistance, and can still maintain the particle state after being stirred in a batch stirred tank reactor for 5 hours without obvious broken phenomenon. The catalyst of the invention has good catalytic activity and can be reused, and the yield of ethylene glycol monobutyl ether reaches 36%.
Description
Technical field
The present invention relates to a kind of mesoporous molecular sieve catalyst, the invention still further relates to the application process of this mesoporous molecular sieve catalyst in the synthesizing glycol monobutyl ether.
Background technology
Minimize for catalyst residualinternal stress of himself in preparation and use is reached, catalyst must be shaped to the particle of definite shape and size in the preparation, and this molding procedure is a committed step in the catalyst commercial production.Existing shaping of catalyst method kind is a lot; Common have (Ruthven D M. such as compression forming method, extruded moulding method, rotational forming method, spray shaping method, the honeycomb type method of forming; Etc.J.Wiley-Interscience; New York; 1984), said method has different features and purposes separately.
In the shaping of catalyst process, introducing proper additive is the effective way that reduces residualinternal stress in the catalyst, thereby in recent years the relation between the variation of the character that adds additive in the forming process, condition of molding and catalyst mechanical strength, the pore structure is received people's attention day by day.Jiratov has proposed the function that in the forming process peptization property of peptizing agent is the acid factor of Hammett, finds that simultaneously the Aci-Jel solvent can obviously improve catalyst strength, improves pore structure.Existing result of study shows; The binder component medium viscosity is bigger with sesbania powder concentration change; Add the sesbania powder in the forming process and help moulding (Li Y Y.; Etc.J.Powder Technology.2001 (116): 85～96), but so far the relation of condition of molding and catalyst chemical performance impact is not seen play-by-play as yet.
Glycol ether is the important derivatives of oxirane, because of its molecule contains ether and hydroxyl, with its excellent performance, is widely used as solvent, jet fuel anti-freezing agent, brake-fluid, chemical intermediate.Gylcol ether mainly comprises ethylene glycol first (second, fourth) ether, diethylene glycol first (second, fourth) ether and triethylene glycol first (second, fourth) ether etc.There is gylcol ether more than 50% to be used as the solvent of various industrial process, wherein having the call approximately with butyl glycol ether and acetate thereof.
In the series of products of glycol ether, EGME is surface of good paint solvent and military jet fuel freezing point depressant; Ethylene glycol ethyl ether and acetate thereof also can be made the cleaning agent of metal and glass mainly as the industrial solvent of protective coating, dyestuff, resin, leather etc.; Butyl glycol ether and acetate thereof have good dispersiveness in water, be widely used in the water based paint.In addition, gylcol ether can also be used for many fields such as cosmetics industry, perfume industry, medical industry, oil field chemical.Each application has proposed more and more higher requirement to the character and the application performance of glycol ether series of products; Know at present; Influencing the molecular weight of product topmost factor that distributes is the structure of start material and the character of catalyst; Thereby after the kind of having confirmed start material, the key factor that the character of catalyst has just become the decision molecular weight of product to distribute.The Al-MCM-41 mesoporous molecular sieve catalyst can improve the character and the application performance of glycol ether series of products through the glycol ether molecular weight distribution that narrows.
Summary of the invention
The technical problem that the present invention will solve is to provide a kind of mesoporous molecular sieve catalyst, and this catalyst has not only that compressive resistance is good, the anti-fight performance, and possesses good catalytic activity.The another one technical problem that the present invention will solve is to provide the application process of a kind of this mesoporous molecular sieve catalyst in the synthesizing glycol monobutyl ether.
Mesoporous molecular sieve catalyst of the present invention is to adopt following method to prepare moulding:
1. a certain amount of mesopore molecular sieve Al-MCM-41 of weighing puts into mortar;
2. add the gama-alumina with respect to mesopore molecular sieve Al-MCM-4 weight 30～40%, fully mix, grinding is sieved;
3. the weight ratio by relative mesopore molecular sieve Al-MCM-41 weight 10%～12%, 3%～5% and 5%～7% takes by weighing HNO respectively
3, polybasic carboxylic acid and three kinds of auxiliary agents of Macrogol 6000, and join in the step mixed-powder 2.;
4. above-mentioned all raw material stirring are even, putting into banded extruder after fully mixing, to be squeezed into diameter be 3～5mm, and length is the rectangular of 5～8mm, and room temperature held 2h dries.Be put into 100
oDry 10h in the C drying box sends into 550～600 ℃ of roasting 5h in the Muffle furnace, obtains the preformed catalyst finished product.This catalyst average pore size is about 4 nm, and specific area is 800～1000 m
2G
-1
Utilize the application of mesoporous molecular sieve catalyst in the synthesizing glycol monobutyl ether of said method moulding:
Catalyst amount is 5%～7% of a quality of glycol; Ethylene glycol and catalyst are joined autoclave; Nitrogen protection; The reaction initial pressure is 0.4 MPa～0.5 Mpa; When temperature is increased to 110 ℃～120 ℃ of regulation reaction temperatures; Gradation adds the oxirane (EO) of metering, when reaction proceeds to pressure and no longer obviously descends, stops to react cooling discharge.
Advantage of the present invention is: the present invention is to analyzing at the Al-MCM-41 of different condition compacted under molecular sieve, system thinking the influence of condition of molding to catalyst acid amount, pore passage structure, side pressure strength etc.Mesoporous molecular sieve catalyst macroscopic view rerum natura through the test proof adopts this method to process is best, and its maximum side pressure strength can reach 48Ncm
-1, total acid content can reach 0.8201mmolg
-1, weak to middle strong acidity.Have that intensity is good, the anti-fight performance, in batch stirred tank reactors, stir and still can keep graininess in 5 hours, do not have obvious broken phenomenon.Catalyst of the present invention has good catalytic activity in the reaction of synthesizing glycol monobutyl ether, and can reuse, and the ethylene glycol monobutyl ether yield reaches 36%.When catalyst amount is 5%～7% of a quality of glycol, reaction temperature is 110 ℃～120 ℃, and the reaction initial pressure is 0.4 MPa～0.5 Mpa, and the Mean Speed of catalytic reaction reaches 2.604mol.h
-1.mol
-1
Description of drawings
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described in detail.
Fig. 1 is the XRD figure before the shaping of catalyst of the present invention.
Fig. 2 is the XRD figure behind the shaping of catalyst of the present invention.
Fig. 3 is the sem analysis figure before the shaping of catalyst of the present invention.
Fig. 4 is the sem analysis figure behind the shaping of catalyst of the present invention.
Fig. 5 is the NH before the shaping of catalyst of the present invention
3-TPD analysis chart.
Fig. 6 is the NH before the shaping of catalyst of the present invention
3-TPD analysis chart.
Fig. 7 is the influence of gama-alumina consumption to the molded molecular sieve side pressure strength.
Fig. 8 is the correlation diagram of reaction temperature and reaction rate among the embodiment 3.
Fig. 9 be among the embodiment 4 initial pressure to the correlation diagram of reaction rate.
Figure 10 be among the embodiment 5 catalyst amount to the correlation diagram of reaction rate.
The specific embodiment
The moulding of embodiment 1:Al-MCM-41 mesoporous molecular sieve catalyst
With mol ratio n (TEOS): n (NaAlO
2): n (CTAB): n (H
2O)=and 1.0:0.033:0.012:3.5:130, synthesize the Al-MCM-41 mesopore molecular sieve.At ambient temperature with a certain amount of NaAlO
2(about 0.7g) and be dissolved in the deionized water of 600ml in softex kw CTAB (about 12g) adds ethylenediamine, transfers system pH=12, stirs in middling speed (300 rad/min) at last to add the 57ml ethyl orthosilicate down, reacts 7h down at 50 ℃.After reacting end, leave standstill cool to room temperature, the about 15h of crystallization sedimentation, suction filtration are also extremely neutral with its washing with deionized water, and solid is dry 12h under 100 ℃.Place 550 ℃ of Muffle furnace roasting 6h then, obtain the Al-MCM-41 mesopore molecular sieve.
The moulding of embodiment 2:Al-MCM-41 mesoporous molecular sieve catalyst
1. a certain amount of mesopore molecular sieve Al-MCM-41 of weighing puts into mortar.
2. add gama-alumina,
W(gama-alumina)=40% (Al-MCM-41) fully mixes, and grinding is sieved.
3. three kinds of auxiliary agents of weighing,
W(HNO
3)=10%,
W(polybasic carboxylic acid)=3% draw
W(Macrogol 6000)=5% is in mixed-powder.
4. stir, put into the banded extruder extruded moulding after fully mixing, obtain long 5～8mm, the particle of diameter 3～5mm, room temperature held 2h dries, 100
oDry 10h in the C drying box, 550 ℃ of roasting 5h obtain the preformed catalyst finished product.
Attaching Fig. 1 and 2 is respectively the XRD figure before and after the moulding of Al-MCM-41 mesoporous molecular sieve catalyst.Before can finding out the Al-MCM-41 moulding
d 100=3.425nm,
d 110=1.463nm,
d 200=1.342nm.After the moulding
d 100=3.221 nm,
d 110=1.678 nm,
d 200=1.252 nm.After the moulding with moulding before sample compare, though the minute surface pitch smaller, hole wall thickness degree increases moulding and does not change catalyst crystal structure, has still kept regular hexagonal mesoporous architectural feature.
Accompanying drawing 3 and 4 is respectively the NH before and after the moulding of Al-MCM-41 mesoporous molecular sieve catalyst
3-TPD spectrogram.Can find out that there is a weak acid center in this catalyst, the acid amount of moulding rear catalyst is 0.8201mmolg
-1, with the acid amount (0.70421mmolg before the moulding
-1) compare, the acid amount is improved to some extent.
Accompanying drawing 5 and 6 is respectively to the sem analysis before and after the moulding of Al-MCM-41 mesoporous molecular sieve catalyst.Can contrast the Al-MCM-41 molecular sieve catalyst of finding out after the moulding compares with the preceding catalyst raw powder of moulding; Catalyst after the moulding has bigger particle and duct; Can improve the mass transfer and the heat transfer of reaction, help the carrying out of catalytic reaction and be prone to separating with the end product of reaction.
Accompanying drawing 7 is the influence of gama-alumina consumption to the molded molecular sieve side pressure strength, therefrom can find out when binder dosage be catalyst 30%～40% the time, the pressure measurement intensity of molecular sieve is tending towards the highest equilibrium valve.
Embodiment 3: the reaction rate (be decided by reaction temperature) of moulding Al-MCM-41 in the reaction of catalytically synthesizing glycol monobutyl ether
In the autoclave that mechanical stirring device and water-cooling apparatus are housed, add 1mol (a certain amount of) ethylene glycol,
W(cat) %=5% (ethylene glycol) (catalytic amount be ethylene glycol 5%～7%) when being heated to 140 ℃, adds 1mol oxirane in batches, and initial pressure is 0.45Mpa, and this moment, reacting ethylene oxide speed was 2.756mol.h
-1.mol
-1
Accompanying drawing 8 can find out that temperature has very big influence to reaction rate, selects suitable temperature, helps the raising of product yield.(be lower than 110 ℃) at a lower temperature, the reaction of ethylene glycol and EO is very slow; In temperature during greater than 110 ℃; Rising along with temperature; Reaction rate has significantly and to promote, but with the further rising of temperature, amplification reduces gradually; When temperature has had higher reaction rate during at 120 ℃; Simultaneously, the too high generation that can increase side reaction of reaction temperature, the product color obviously deepens; This is because due to the increase of accessory substance PEG content, so can select 11 ℃～120 ℃ for use as reaction temperature.
Embodiment 4: the reaction rate (be decided by initial pressure) of moulding Al-MCM-41 in the reaction of catalytically synthesizing glycol monobutyl ether
In the autoclave that mechanical stirring device and water-cooling apparatus are housed, add 1mol ethylene glycol,
W(cat) %=5～7% (ethylene glycol) (catalytic amount be ethylene glycol 5%～7%), reaction temperature is 110 ℃～120 ℃, adds 1mol oxirane in batches, and initial pressure is 0.65Mpa, and this moment, reacting ethylene oxide speed was 3.132mol.h
-1.mol
-1
Accompanying drawing 9 can be found out; The initial pressure of reaction system has bigger influence to reaction rate; Along with the increase reaction rate of system pressure obviously increases; When the value of initial pressure increases to increasing not obvious to the above afterreaction speed of 0.50Mpa; Because the excessive reaction of reaction system pressure is too violent, the reaction temperature too fast meeting of rising causes side reaction to increase.The excessive requirement to reactor of reaction system pressure simultaneously is also high, and therefore, this experimental selection reaction initial pressure is 0.45～0.50Mpa.
Embodiment 5: the reaction rate (be decided by catalyst amount) of moulding Al-MCM-41 in the reaction of catalytically synthesizing glycol monobutyl ether
In the autoclave that mechanical stirring device and water-cooling apparatus are housed, add 100g ethylene glycol,
W(cat) %=10% (ethylene glycol) (catalytic amount be ethylene glycol 9%～10%), reaction temperature is 110 ℃～120 ℃, adds 1mol oxirane in batches, and initial pressure is 0.45Mpa, and this moment, reacting ethylene oxide speed was 3.476mol.h
-1.mol
-1
Accompanying drawing 10 can be found out; Increase along with catalyst amount; Reaction rate accelerates; When catalyst amount reaction rate increasing degree greater than 5% time is slowed down to some extent; And all need certain technology and financial cost in the synthetic and forming process of catalyst; So catalyst consumption is unsuitable excessive, the selecting catalyst consumption be quality of glycol 5%～7% as optimum condition.
Embodiment 6: glycol monoethyl ether yield in the reaction of moulding Al-MCM-41 catalytically synthesizing glycol monobutyl ether
In the autoclave that mechanical stirring device and water-cooling apparatus are housed, add 100g ethylene glycol,
W(cat) %=5% (ethylene glycol) (catalytic amount be ethylene glycol 5%～7%), reaction temperature is 110 ℃～120 ℃, adds 1mol oxirane in batches, and initial pressure is 0.45Mpa, and this moment, the glycol monoethyl ether yield was 36%.
Embodiment 7: activation of moulding Al-MCM-41 mesoporous molecular sieve catalyst and regenerability
The ethylene glycol monobutyl ether synthetic reaction finishes, and through filtration under diminished pressure the catalyst in the product is leached, and uses deionized water drip washing, and dry under 100 ℃, 600 ℃ of following roastings are weighed, and calculate catalyst recovery yield.Catalyst amount is 5 %～7% of quality of glycol, is 110 ℃～120 ℃ in temperature, and initial pressure is 0.4MPa～0.5 Mpa, and reusing four catalyst synthesizing glycol monomethyl ether average response speed is 2.42 mol.h
-1.mol
-1
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| CN103087676A (en) * | 2013-01-29 | 2013-05-08 | 淄博理研泰山涂附磨具有限公司 | Sintering method of abrasion resisting abrasive particles |
| CN104549552A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for balling molecular sieve |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275440A (en) * | 1999-05-26 | 2000-12-06 | 辽阳利迪化学品有限公司 | Chromatographic column molecular sieve catalyst for synthesizing glycol serier monoethers and diethyl glycol monoethers |
| KR100926800B1 (en) * | 2008-03-28 | 2009-11-12 | 한국화학연구원 | Catalyst for synthesizing dimethyl ether by dehydration of methanol, preparation method thereof and preparation method for dimethyl ether |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1275440A (en) * | 1999-05-26 | 2000-12-06 | 辽阳利迪化学品有限公司 | Chromatographic column molecular sieve catalyst for synthesizing glycol serier monoethers and diethyl glycol monoethers |
| KR100926800B1 (en) * | 2008-03-28 | 2009-11-12 | 한국화학연구원 | Catalyst for synthesizing dimethyl ether by dehydration of methanol, preparation method thereof and preparation method for dimethyl ether |
Non-Patent Citations (1)
| Title |
|---|
| 宋伟眀等: "Al-MCM-41介孔分子筛在辛醇乙氧基化反应中的催化性能", 《化学反应工程与工艺》, vol. 21, no. 3, 30 June 2005 (2005-06-30), pages 257 - 262 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103087676A (en) * | 2013-01-29 | 2013-05-08 | 淄博理研泰山涂附磨具有限公司 | Sintering method of abrasion resisting abrasive particles |
| CN103087676B (en) * | 2013-01-29 | 2014-07-30 | 淄博理研泰山涂附磨具有限公司 | Sintering method of abrasion resisting abrasive particles |
| CN104549552A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for balling molecular sieve |
| CN104549552B (en) * | 2013-10-29 | 2016-08-10 | 中国石油化工股份有限公司 | A kind of method of molecular sieve balling-up |
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| CN102350371B (en) | 2013-04-24 |
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