CN107915576A - By the method for ethylene carbonate ester hydrolysis production ethylene glycol - Google Patents
By the method for ethylene carbonate ester hydrolysis production ethylene glycol Download PDFInfo
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- CN107915576A CN107915576A CN201610878288.1A CN201610878288A CN107915576A CN 107915576 A CN107915576 A CN 107915576A CN 201610878288 A CN201610878288 A CN 201610878288A CN 107915576 A CN107915576 A CN 107915576A
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- ethylene carbonate
- catalyst
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- ethylene glycol
- ethylene
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 115
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000010931 ester hydrolysis Methods 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000011574 phosphorus Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000969 carrier Substances 0.000 claims abstract description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 9
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- -1 solve the problems Chemical compound 0.000 abstract description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 101000611023 Homo sapiens Tumor necrosis factor receptor superfamily member 6 Proteins 0.000 description 10
- 102100040403 Tumor necrosis factor receptor superfamily member 6 Human genes 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 235000019838 diammonium phosphate Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000036571 hydration Effects 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 101000679903 Homo sapiens Tumor necrosis factor receptor superfamily member 25 Proteins 0.000 description 4
- 102100022203 Tumor necrosis factor receptor superfamily member 25 Human genes 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/83—Aluminophosphates [APO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method by ethylene carbonate ester hydrolysis production ethylene glycol, mainly solve the problems, such as the prior art there are poor catalyst stability, active component to be easy to run off.The present invention by using including at reaction conditions, ethylene carbonate and water are contacted with catalyst the step of；The catalyst is in terms of parts by weight including following component：A) 1~50 part of niobium pentaoxide；And b) technical solution of 50~99 parts of phosphorus alumina APO carriers preferably solves the problems, such as this, available in the industrial production of preparing ethyl glycol by hydrolysis of ethylene carbonate.
Description
Technical field
The present invention relates to a kind of method by ethylene carbonate ester hydrolysis production ethylene glycol.
Background technology
The hydrolysis of esters is a kind of important chemical reaction, is widely used in the every field of petrochemical iy produced, its middle ring
The hydrolysis of shape carbonic ester, such as ethylene carbonate (EC), propene carbonate is even more to have very important fundamental position.
The hydrolysis of EC is by the important step of ethylene oxide (EO) catalysis hydration two-step method production ethylene glycol (EG).EG is one
The important Organic Chemicals of kind, is mainly used to produce polyester fiber, antifreezing agent, unsaturated polyester resin, non-ionic surface work
Property agent, monoethanolamine and explosive etc..The production technology of EG is broadly divided into petrochemical industry route and non-petrochemical industry route.Have in petrochemical industry route
EO direct hydration methods and EO catalytic hydrations, direct hydration method need higher water ratio (being more than 20) just to can guarantee that higher EG
Yield, and it is higher to consume energy during purifying EG.EO catalytic hydrations include direct catalytic hydration and EC routes again.Directly urge
Change hydration method water than relatively low (about 5 or so), but still need evaporation and remove substantial amounts of water, and EC routes are then first with second
Alkene aoxidizes the CO discharged during EO processed2EC is generated under the action of catalyst for raw material and EO, is then catalyzed by intermediate product of EC
Hydrolysis generation EG, the process water ratio are the industrialization directions of EO EG from now on close to stoichiometric ratio 1.
The catalyst for having been used for annular carbonic acid esters hydrolysis at present mainly has：Alkali (soil) metal carbonate (hydrogen) salt
(US4524224,1985), Mo and W compound (JP822106631,1982；WO2009071651,2009), quaternary ammonium salt, season
Ammonium salt and ion exchange resin (EP0133763,1989；US6080897,2000；US20090156867,2009) etc..But these
More or less there are the problems such as catalyst separation is difficult, activity is low, stability is not high for catalyst system and catalyzing.
It is all preferable that strong base ion exchange resin is used for activity and selectivity during annular carbonic acid esters hydrolysis, but since its is resistance to
Gentle swelling resistance poor performance, activity declines very fast (Yu FP, Cai H, He WJ, et in catalytic reaction process
al.J.Appl.Polym.Sci.,2010,115:2946~2954), this is to cause the catalyst to fail industrialized main original
Cause.
The content of the invention
The technical problems to be solved by the invention are that there are poor catalyst stability, active component to be easy to run off for the prior art
A kind of problem, there is provided new method by ethylene carbonate ester hydrolysis production ethylene glycol.This method has catalyst activity and selection
Property high, the characteristics of active component not easily runs off.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：One kind is produced by ethylene carbonate ester hydrolysis
The step of method of ethylene glycol, including at reaction conditions, ethylene carbonate and water are contacted with catalyst；The catalyst is with weight
Amount number meter includes following component：A) 1~50 part of niobium pentaoxide；And b) 50~99 parts of phosphorus alumina APO carriers.
In above-mentioned technical proposal, the content of niobium pentaoxide is preferably 5~30 parts, and the content of phosphorus alumina APO carriers is preferred
For 70~95 parts.
In above-mentioned technical proposal, in phosphorus alumina APO carriers, the weight content of Al is with Al2O310~80% are calculated as, is preferably
20~60%；The content of P is with P2O520~90% are calculated as, is preferably 40~80%.
In above-mentioned technical proposal, reaction temperature is 60~200 DEG C, is preferably 80~160 DEG C, more preferably 100~140
℃。
In above-mentioned technical proposal, the molar ratio of water and ethylene carbonate is (1~10):1, be preferably (1~8):1, it is more excellent
Elect as (1~6):1.
In above-mentioned technical proposal, the weight ratio of catalyst and ethylene carbonate is (0.005~1):1, be preferably (0.01~
0.5):1, more preferably (0.02~0.2):1.
The preparation method of heretofore described catalyst is as follows：Phosphorus alumina APO is added in the oxalic acid solution of niobic acid, dried
Up to the niobium pentaoxide catalyst n APO of phosphorus alumina load after dry, roasting.Drying temperature is 100~150 DEG C, and drying time is
5~24 it is small when.Calcination temperature is 550~650 DEG C, when roasting time is 1~24 small.Wherein described phosphorus alumina carrier is aluminium oxide
With the mixed oxide of phosphorous oxide.Its preparation method is to be known in the art, can be prepared with the following method：1) room temperature
Under, by aluminum nitrate (Al (NO3)3·9H2O) and diammonium hydrogen phosphate is soluble in water, then adds concentrated nitric acid and is acidified the solution, obtains
Solution A；2) concentrated ammonia liquor at room temperature, is added into solution A and adjusts pH value to 8, the precipitation of formation is filtered, washing, dry, roasting
Up to the phosphorus alumina APO.Drying temperature is 100~150 DEG C, when drying time is 5~24 small.Calcination temperature is 550~650
DEG C, when roasting time is 1~24 small.The addition of concentrated nitric acid is the 5~20% of aluminum nitrate weight.
Carrier used in the present invention is phosphorus alumina, and compared with ion exchange resin, heat resistance greatly improves；Used
Active component niobium pentaoxide property stablize, it is acid suitable, solve poor catalyst stability present in conventional art, work
The problem of property component is easy to run off.Using the method for the present invention, in 100 DEG C of reaction temperature, the molar ratio of water and ethylene carbonate is
1.5:1, the weight ratio of catalyst and ethylene carbonate is 0.05：Under the conditions of 1, the conversion ratio of ethylene carbonate is 99.3%, second
The selectivity of glycol is 99.5%, and after catalyst is reused 5 times, activity is dropped by less than 5%, achieves preferable technology effect
Fruit.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
The preparation of phosphorus alumina APO：At room temperature, 58.8g aluminum nitrates and 22.3g diammonium hydrogen phosphates are dissolved in 500ml deionizations
In water, after stirring 1h, after adding the acidifying of 10ml concentrated nitric acids, continue to be added dropwise concentrated ammonia liquor adjusting pH value to 8, by the precipitation of formation
Filter, is dried overnight at 120 DEG C after being washed with deionized 3 times, then in 500 DEG C of drying and roastings, obtains phosphorus alumina APO-1, passes through
ICP-AES is measured, and the weight content of the Al in APO-1 is with Al2O3The weight content of 40%, P is calculated as with P2O5It is calculated as 60%.
【Embodiment 2】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 14.7g and 33.5g, obtain phosphorus alumina APO-2, measured through ICP-AES, the weight content of the Al in APO-2 is with Al2O3Meter
For 10%, P weight content with P2O5It is calculated as 90%.
【Embodiment 3】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 36.8g and 27.9g, obtain phosphorus alumina APO-3, measured through ICP-AES, the weight content of the Al in APO-3 is with Al2O3Meter
For 25%, P weight content with P2O5It is calculated as 75%.
【Embodiment 4】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 73.5g and 18.6g, obtain phosphorus alumina APO-4, measured through ICP-AES, the weight content of the Al in APO-4 is with Al2O3Meter
For 50%, P weight content with P2O5It is calculated as 50%.
【Embodiment 5】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 95.6g and 13.0g, obtain phosphorus alumina APO-5, measured through ICP-AES, the weight content of the Al in APO-5 is with Al2O3Meter
For 65%, P weight content with P2O5It is calculated as 35%.
【Embodiment 6】
The preparation process of phosphorus alumina APO with【Embodiment 1】Identical, simply the amount of aluminum nitrate used and diammonium hydrogen phosphate is divided
Not Wei 117.6g and 7.4g, obtain phosphorus alumina APO-6, measured through ICP-AES, the weight content of the Al in APO-6 is with Al2O3Meter
For 80%, P weight content with P2O5It is calculated as 20%.
【Embodiment 7】
Weigh 2.67g niobic acids to be dissolved in the oxalic acid solution that 50ml concentration is 1.8mol/L, add 10g phosphorus alumina APO-1, obtain
To mixture be dried overnight at 120 DEG C, then 500 DEG C roast 2h obtain phosphorus alumina load niobium pentaoxide catalyst
The weight content of NAPO-1, wherein niobium pentaoxide are 20%, and the weight content of phosphorus alumina APO-1 is 80%.
【Embodiment 8】
Method for preparing catalyst is same【Embodiment 7】, simply the quality of niobic acid used is 0.56g, obtains the load of phosphorus alumina
Niobium pentaoxide catalyst n APO-2, wherein the weight content of niobium pentaoxide be 5.1%, the weight of phosphorus alumina APO-1 contains
Measure as 94.9%.
【Embodiment 9】
Method for preparing catalyst is same【Embodiment 7】, simply the quality of niobic acid used is 1.19g, obtains the load of phosphorus alumina
Niobium pentaoxide catalyst n APO-3, wherein the weight content of niobium pentaoxide be 10.0%, the weight of phosphorus alumina APO-1 contains
Measure as 90.0%.
【Embodiment 10】
Method for preparing catalyst is same【Embodiment 7】, simply the quality of niobic acid used is 0.22g, obtains the load of phosphorus alumina
Niobium pentaoxide catalyst n APO-4, wherein the weight content of niobium pentaoxide be 2.1%, the weight of phosphorus alumina APO-1 contains
Measure as 97.9%.
【Embodiment 11】
Method for preparing catalyst is same【Embodiment 7】, simply the quality of niobic acid used is 4.58g, obtains the load of phosphorus alumina
Niobium pentaoxide catalyst n APO-5, wherein the weight content of niobium pentaoxide be 31.0%, the weight of phosphorus alumina APO-1 contains
Measure as 69.0%.
【Embodiment 12】
Method for preparing catalyst is same【Embodiment 7】, simply the quality of niobic acid used is 7.12g, obtains the load of phosphorus alumina
Niobium pentaoxide catalyst n APO-6, wherein the weight content of niobium pentaoxide be 39.0%, the weight of phosphorus alumina APO-1 contains
Measure as 69.0%.
【Embodiment 13】
Method for preparing catalyst is same【Embodiment 7】, simply carrier used is APO-2, obtains five oxygen of phosphorus alumina load
Change two niobium catalytic NAPO-7.
【Embodiment 14】
Method for preparing catalyst is same【Embodiment 7】, simply carrier used is APO-3, obtains five oxygen of phosphorus alumina load
Change two niobium catalytic NAPO-8.
【Embodiment 15】
Method for preparing catalyst is same【Embodiment 7】, simply carrier used is APO-4, obtains five oxygen of phosphorus alumina load
Change two niobium catalytic NAPO-9.
【Embodiment 16】
Method for preparing catalyst is same【Embodiment 7】, simply carrier used is APO-5, obtains five oxygen of phosphorus alumina load
Change two niobium catalytic NAPO-10.
【Embodiment 17】
Method for preparing catalyst is same【Embodiment 7】, simply carrier used is APO-6, obtains five oxygen of phosphorus alumina load
Change two niobium catalytic NAPO-11.
【Embodiment 18】
Will【Embodiment 7】Prepared catalyst n APO-1 is used in the reaction of preparing ethyl glycol by hydrolysis of ethylene carbonate.
44.0 grams of ethylene carbonates, 13.5 grams of deionized waters and 2.2 grams of NAPO-1 are placed in (water and ethylene in 100 milliliters of autoclaves
The molar ratio of enester is 1.5：1, the mass ratio of catalyst and ethylene carbonate is 0.05：1) when, 100 DEG C of reactions 2 are small.Reaction knot
Shu Hou, autoclave is cooled to room temperature, emptying.Take liquid product to carry out gas chromatographic analysis, measure the conversion of ethylene carbonate
Rate is 99.3%, and the selectivity of ethylene glycol is 99.5%, remaining is more ethylene glycol.
【Embodiment 19~28】
Will【Embodiment 8~17】Obtained catalyst n APO-2~NAPO-11 is used for ethylene carbonate ester hydrolysis and prepares second
In the reaction of glycol, reaction condition with【Embodiment 18】Identical, obtained reaction result is as shown in table 1.
Table 1
【Embodiment 29】
Together【Embodiment 18】, simply reaction temperature is 120 DEG C.The conversion ratio for obtaining ethylene carbonate is 99.3%, second two
The selectivity of alcohol is 99.0%, and the selectivity of more ethylene glycol is 1.0%.
【Embodiment 30】
Together【Embodiment 18】, simply reaction temperature is 140 DEG C.The conversion ratio for obtaining ethylene carbonate is 99.5%, second two
The selectivity of alcohol is 98.1%, and the selectivity of more ethylene glycol is 1.9%.
【Embodiment 31】
Together【Embodiment 18】, simply reaction temperature is 80 DEG C.The conversion ratio for obtaining ethylene carbonate is 51.2%, ethylene glycol
Selectivity be 99.3%, the selectivity of more ethylene glycol is 0.7%.
【Embodiment 32】
Together【Embodiment 18】, simply the quality of deionized water be 27.0 grams (molar ratio of water and ethylene carbonate is 3：1).
It is 99.5% to obtain ethylene carbonate ester conversion rate, and the selectivity of ethylene glycol is 99.3%, and the selectivity of more ethylene glycol is 0.7%.
【Embodiment 33】
Together【Embodiment 18】, simply the quality of deionized water be 72.0 grams (molar ratio of water and ethylene carbonate is 8：1).
It is 99.7% to obtain ethylene carbonate ester conversion rate, and the selectivity of ethylene glycol is 99.4%, and the selectivity of more ethylene glycol is 0.6%.
【Embodiment 34】
Together【Embodiment 18】, simply the dosage of catalyst be 1.1 grams (ratio of catalyst and ethylene carbonate is 0.025：
1).It is 65.3% to obtain ethylene carbonate ester conversion rate, and the selectivity of ethylene glycol is 99.2%, and the selectivity of more ethylene glycol is
0.8%.
【Embodiment 35】
Together【Embodiment 18】, simply catalyst amount be 8.8 grams (ratio of catalyst and ethylene carbonate is 0.2：1).
It is 99.8% to obtain ethylene carbonate ester conversion rate, and the selectivity of ethylene glycol is 98.7%, and the selectivity of more ethylene glycol is 1.3%.
【Embodiment 36】
Together【Embodiment 18】, simply (mass ratio of catalyst and ethylene carbonate is the quality of catalyst for 17.6 grams
0.4：1).It is 99.9% to obtain ethylene carbonate ester conversion rate, and the selectivity of ethylene glycol is 97.3%, and the selectivity of more ethylene glycol is
2.7%.
【Embodiment 37】
Will【Embodiment 18】Catalyst after reaction is separated, by with【Embodiment 18】Same reaction conditions are applied mechanically
5 times, activity is not decreased obviously.Reaction result is shown in Table 2.
Table 2
Claims (7)
1. a kind of method by ethylene carbonate ester hydrolysis production ethylene glycol, including at reaction conditions, ethylene carbonate and water with
The step of catalyst contacts；The catalyst is in terms of parts by weight including following component：A) 1~50 part of niobium pentaoxide；With
B) 50~99 parts of phosphorus alumina APO carriers.
2. according to claim 1 by the method for ethylene carbonate ester hydrolysis production ethylene glycol, it is characterised in that niobium pentaoxide
Content be 5~30 parts, the contents of phosphorus alumina APO carriers is 70~95 parts.
3. according to claim 1 by the method for ethylene carbonate ester hydrolysis production ethylene glycol, it is characterised in that phosphorus alumina APO
In carrier, the weight content of Al is with Al2O3The content of 10~80%, P is calculated as with P2O5It is calculated as 20~90%.
4. according to claim 3 by the method for ethylene carbonate ester hydrolysis production ethylene glycol, it is characterised in that phosphorus alumina APO
In carrier, the weight content of Al is with Al2O3The content of 20~60%, P is calculated as with P2O5It is calculated as 40~80%.
5. according to claim 1 by the method for ethylene carbonate ester hydrolysis production ethylene glycol, it is characterised in that reaction temperature is
60~200 DEG C, the molar ratio of water and ethylene carbonate is (1~10):1, the weight ratio of catalyst and ethylene carbonate is
(0.005~1):1.
6. according to claim 5 by the method for ethylene carbonate ester hydrolysis production ethylene glycol, it is characterised in that reaction temperature is
80~160 DEG C, the molar ratio of water and ethylene carbonate is (1~8):1, the weight ratio of catalyst and ethylene carbonate is (0.01
~0.5):1.
7. according to claim 6 by the method for ethylene carbonate ester hydrolysis production ethylene glycol, it is characterised in that reaction temperature is
100~140 DEG C, the molar ratio of water and ethylene carbonate is (1~6):1, the weight ratio of catalyst and ethylene carbonate is (0.02
~0.2):1.
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| CN112439434A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Ethylene glycol hydrofining agent and application thereof |
| CN112439434B (en) * | 2019-09-02 | 2023-08-29 | 中国石油化工股份有限公司 | Glycol hydrofining agent and application thereof |
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