CN107626320A - Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and preparation method and application - Google Patents
Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and preparation method and application Download PDFInfo
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- CN107626320A CN107626320A CN201710944320.6A CN201710944320A CN107626320A CN 107626320 A CN107626320 A CN 107626320A CN 201710944320 A CN201710944320 A CN 201710944320A CN 107626320 A CN107626320 A CN 107626320A
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Abstract
The present invention relates to a kind of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and preparation method and application, preparation method, comprise the following steps：Soluble copper salt, soluble rare earth metal salt and soluble zirconates are added into acetic acid solution, stirs to metal salt and is completely dissolved, obtain mixed solution；Mixed solution is dried, obtains catalyst precursor powder；Catalyst precursor powder is calcined, obtains solid particle；Solid particle is ground, obtains oxalic ester hydrogenation synthesizing of ethylene glycol catalyst.The present invention is using the acetic acid complexometry combination solvent evaporation of simple environment protection, economy and facility, the rear-earth-doped CuO/ZrO of one pot of stratiform being prepared2Catalyst, there is the catalytic activity and stability of good oxalate selection hydrogenation preparing ethylene glycol, the industrialized production available for ethylene glycol；And preparation process is easy, without step, the inactive component loss such as washing, filtering；Raw material is cheap and easy to get.
Description
Technical field
The present invention relates to catalyst preparation technical field, and in particular to a kind of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst and
Its preparation method and application.
Background technology
With world petroleum resource increasingly depleted and to Coal Clean, efficiently utilize demand increasingly increase, develop with
Coal and biomass prepare multi-chemical for basic chemical raw materials and have become extensive common recognition on a large scale, meet social demand
Needed with environmental protection.At present, oxalate is produced by synthesis gas obtained by coal and gasification of biomass and has been realized in industrialized production,
And the demand in market can be ensured.Thermodynamics of reactions is analyzed and numerous results of study show that oxalate catalytic hydrogenation can give birth to
Into intermediate product methyl glycollate, and methyl glycollate is further hydrogenated to end-product ethylene glycol or ethanol, so the technology
As the focus researched and developed at present.
Noble metal catalyst has higher activity to catalysis ester through hydrogenation reaction.Such as compare because Au and Ag has for C=O
High selection hydrogenation activity, Xiamen University Yuan You pearls load caused synergy after Au-Ag bimetallics with SBA-15, in ester plus
Excellent performance is shown in hydrogen reaction.The cooperations such as his Tsang with Oxford University's Wolfson's catalytic center, by Ni@Ag cores
Core/shell nanoparticles also achieve preferable effect by simply impregnating in embedded SBA-15 in oxalate hydrogenation.But
The with high costs of noble metal catalyst, stability are poor, and its stronger hydrogenolysis is from adsorption capacity and C-C scission of link abilities so that
Product is distributed more widely, accessory substance increases, therefore limits its application in hydrogenation of oxalate for preparing ethylene glycol reaction.Therefore, mountain
Western coalification Chen and Zhu separately designed catalyst system and catalyzing using transition metal Co and Ni as active component and applied to grass
Among acid esters hydrogenation reaction, certain effect is achieved, but product is based on methyl glycollate.
Due to many excellent characteristics of copper-based catalysts, domestic and international more units are directed to it in oxalate hydrogen addition technology
Research, the main species including catalyst carrier and auxiliary agent, catalyst pattern etc. to catalytic activity and stability influence.
(1) in view of SiO2Superior characteristic, Fan Kangnian seminars of Fudan University steam the Cu/SiO of method preparation using ammonia2Catalysis
Agent is catalyzed oxalate hydrogenolysis, and the yield of ethylene glycol can reach 98%.Some reports utilize other carriers such as ZrO2、Al2O3、
The Cu catalyst of hydroxyapatite, activated carbon and CNT even load also shows higher in oxalate hydrogenation
Activity.Change bearer type such as some binary vectors SiO2–TiO2、SiO2–ZrO2Or molecular sieve even load Cu catalyst also obtains
Certain catalytic effect.
(2) use of some electronic auxiliaries or structural promoter is to the composition with certain active Cu base catalyst, catalysis
Performance and stability have a great influence.If Cu-Cr catalyst is in oxalate hydrogenation is catalyzed, there is higher activity and steady
It is qualitative, but Cr is larger to environmental and biological materials harm.By adding appropriate auxiliary agent such as B, Ag, Au, Co, Ni etc. in some reports
Improve Cu/SiO2Stability of the catalyst in oxalate hydrogenation, also achieves certain effect.
(3) catalyst pattern etc. is larger to catalytic activity and stability influence.University Of Tianjin Ma Xinbin and Gong Jinlong etc. with
Cu/SiO2The regular catalyst suitable for commercial Application is prepared for after catalyst coating cordierite, is reduced because air flow method is uneven
Caused by the limitation such as mass transfer, heat transfer.
It although can be very good to be applied in oxalate hydrogenation with certain active Cu bases catalyst, but due to
Some inherent shortcomings be present with certain active Cu bases catalyst, such as using the group that Cu atoms easily occur after a period of time
Poly- and particle growth, drastically reduce active sites reduction, hydrogenation activity.And for example compared to noble metal and other transition metal, Cu
Hydrogenation activity it is not strong, when the diffusion hindered such as mass transfer, heat transfer in reaction, the production capacity of catalyst is also heavily affected.
The content of the invention
For in the prior art the defects of, present invention aims at provide a kind of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst
And preparation method and application, rear-earth-doped, loaded Cu catalyst is prepared with one pot by acetic acid complexometry, makes it in catalysis grass
In the reaction of acid esters hydrogenation synthesizing of ethylene glycol have high oxalic acid ester conversion rate (more than 99%), ethylene glycol yield (98.0%, liquid
When air speed 2.0h-1) and stability (stable operation is more than 240h), it is applicable to actual industrialized production.
To achieve the above object, technical scheme provided by the invention is：
In a first aspect, the invention provides a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, including such as
Lower step：S1：Soluble copper salt, soluble rare earth metal salt and soluble zirconates are added into acetic acid solution, stirred to gold
Category salt is completely dissolved, and obtains mixed solution；S2：Mixed solution is dried, obtains catalyst precursor powder；S3：By catalyst
Precursor powder is calcined, and obtains solid particle；S4：Solid particle is ground, oxalic ester hydrogenation synthesizing of ethylene glycol is obtained and urges
Agent.
It should be noted that the catalyst of oxalic ester hydrogenation synthesizing of ethylene glycol provided by the invention is living based on metallic copper
Property component, ZrO2For carrier, catalyst quality is than composition：Cu content is 5.0~58.0wt%, and the content of rare earth metal is
0.0~5.0wt%, ZrO2Content be 93.8~27.5wt%；The content of wherein metallic copper is preferably 25.0~52.0wt%.
In the further embodiment of the present invention, in step S1, copper, soluble rare earth metal salt in soluble copper salt
In rare earth metal and the atomic ratio of the zirconium in soluble zirconates be (54.3~25.2):1:(543~5.2).
In the further embodiment of the present invention, in step S1, soluble copper salt includes copper nitrate, copper sulphate, carbonic acid
One or more in copper and copper acetate；Soluble zirconates include zirconium nitrate, zirconium sulfate, zirconium carbonate and one kind in acetic acid zirconium or
It is a variety of；Soluble rare earth metal salt includes lanthanum nitrate, lanthanum sulfate, lanthanum carbonate, lanthanum acetate, cerous nitrate, cerous sulfate, cerous carbonate, vinegar
One or more in sour cerium, neodymium nitrate, Dineodymium trisulfate, neodymium carbonate, acetic acid neodymium, praseodymium nitrate, praseodymium sulfate, praseodymium carbonate and praseodymium acetate.
In the further embodiment of the present invention, in step S2, dry temperature is 30~150 DEG C, the dry time
For 2~24h.
In the further embodiment of the present invention, in step S3, calcining specifically includes：By catalyst precursor powder with
1~20 DEG C/min heating rate is warming up to 400~800 DEG C, then calcines 1~10h；In step S4, grinding specifically includes：Will
Solid particle is ground to granularity to 20~120 mesh repeatedly in mortar.
In the further embodiment of the present invention, in step S4, oxalic ester hydrogenation synthesizing of ethylene glycol is obtained after grinding
Before catalyst, in addition to the step of shaping：The product that grinding obtains is molded, the method for shaping is selected from rotational forming, squeezed
Bar is molded and the one or more of compression molding.
Second aspect, the present invention also protect the oxalic ester hydrogenation synthesizing of ethylene glycol being prepared according to the above method to be catalyzed
Agent.
The third aspect, the present invention also protect oxalic ester hydrogenation synthesizing of ethylene glycol catalyst using oxalate hydrogenation synthesis second
Application in glycol.
In the further embodiment of the present invention, the method for application comprises the following steps：S101：Oxalic acid ester through hydrogenation is closed
It is put into ethylene glycol catalyst in fixed bed reactors, in-situ reducing is carried out in pure hydrogen, obtains the Cu with certain activity
Base catalyst；S102：By oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, and with one
The Cu bases catalyst of fixed activity carries out hydrogenation reaction, generates ethylene glycol.
In the further embodiment of the present invention, in step S101, reduction process specifically includes：Adjust the pressure of reduction
For 0~0.5MPa, H is adjusted2Volume space velocity is 200~4000h-1, then it is warming up to 160 with 1~10 DEG C/min heating rate
~300 DEG C, restore 1~6h；In step S102, reaction temperature is 180~260 DEG C, and pressure is 1.2~2.8MPa；Oxalate
The liquid air speed of solution is 0.2~8.0h-1, H2Mol ratio with oxalate is (10~150):1.
Technical scheme provided by the invention, there is following beneficial effect：(1) present invention passes through one pot of system of acetic acid complexometry
Standby rear-earth-doped, loaded Cu catalyst, raw material is cheap and easy to get, and preparation method is simple, without formalities such as filtering, solvent washings, has
Effect avoids the loss of active component；(2) present invention adjusts Cu electronics knot using electronic effect by adding rare earth element
Structure, the anti-caking power of the Cu base catalyst is enhanced, improve the heat endurance of the Supported Cu catalyst；By using spy
Fixed carrier, the second component of addition and the pattern for adjusting catalyst, to reach the inactivation for suppressing Cu base catalyst；Catalyst is special
Different layer structure, be advantageous to the diffusion of heat and quality, reduce diffusional resistance, objectively expand the production energy of catalyst
Power；(3) catalyst that the present invention is prepared has high oxalate in the reaction of catalysis oxalic ester hydrogenation synthesizing of ethylene glycol
Conversion ratio (more than 99%), ethylene glycol yield (98.0%, liquid hourly space velocity (LHSV) 2.0h-1) and stability (stable operation is more than 240h),
That is catalyst productivity and stability is higher, is applicable to actual industrialized production.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by the practice of the present invention.
Brief description of the drawings
Fig. 1 is that the stratiform La being prepared in the embodiment of the present invention one adulterates CuO/ZrO2The SEM figures of catalyst；
Fig. 2 is that the stratiform Ce being prepared in the embodiment of the present invention three adulterates CuO/ZrO2The SEM figures of catalyst；
Fig. 3 is that the stratiform Nd being prepared in the embodiment of the present invention five adulterates CuO/ZrO2The SEM figures of catalyst；
Fig. 4 is that the stratiform Pr being prepared in the embodiment of the present invention seven adulterates CuO/ZrO2The SEM figures of catalyst；
Fig. 5 is that the stratiform Pr being prepared in the embodiment of the present invention nine adulterates CuO/ZrO2The SEM figures of catalyst；
Fig. 6 is that the stratiform La being prepared in the embodiment of the present invention 11 adulterates CuO/ZrO2The SEM figures of catalyst.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes.The following examples are only intended to illustrate the technical solution of the present invention more clearly, therefore is intended only as example, without
It can be limited the scope of the invention with this.
Experimental method in following embodiments, it is conventional method unless otherwise specified.Examination used in following embodiments
Material is tested, is to be commercially available from regular shops unless otherwise specified.Quantitative test in following examples, is respectively provided with three
Secondary to repeat to test, data are to repeat the average value or mean+SD of experiment three times.
Embodiment one
The present embodiment provides a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, comprises the following steps：
S1：12.08g copper nitrates, 0.62g lanthanum acetates and 20.09g zirconium carbonates are added into acetic acid solution, at room temperature
Strong stirring 1h, copper nitrate are completely dissolved, and obtain mixed solution；
S2：Mixed solution is moved into 2h is dried at 120 DEG C, obtain catalyst precursor powder；
S3：Catalyst precursor powder is warming up to 400 DEG C with 10 DEG C/min heating rate, 10h is then calcined, obtains
Solid particle；
S4：By solid particle in mortar repeatedly grinding until granularity be 20 mesh, obtain oxalic ester hydrogenation synthesizing of ethylene glycol
(stratiform La adulterates CuO/ZrO to catalyst2Oxalate hydrogenation catalyst), its pattern is as shown in Figure 1.
Embodiment two
The oxalic ester hydrogenation synthesizing of ethylene glycol catalyst that embodiment one is prepared, for oxalate hydrogenation synthesis second two
In alcohol, concrete application method comprises the following steps：
S101：Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst 1mL is filled in fixed-bed tube reactor, by catalyst
In volume space velocity 2200h-1, 0.5MPa H2300 DEG C are warming up to 1 DEG C/min under atmosphere, reduces 1h at this temperature, is had
There is the Cu base catalyst of certain activity；
S102：It is 180 DEG C, pressure 2.8MPa to adjust reaction temperature, and the liquid air speed of oxalic acid ester solution is 0.2h-1, will
Oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, with being catalyzed with certain active Cu bases
Agent carries out hydrogenation reaction, generates ethylene glycol；Wherein, H2Mol ratio with oxalate is 150:1.
As a result：Under the above-described reaction conditions, the conversion ratio of oxalate is 76.2%, and the selectivity of ethylene glycol is 79.6%,
The selectivity of ethyl glycolate is 18.3%, and the selectivity of ethanol is 2.1%；Catalyst stabilization runs 240h.
Embodiment three
The present embodiment provides a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, comprises the following steps：
S1：21.89g copper sulphate, 1.56g cerous nitrates and 7.54g zirconium nitrates are added into acetic acid solution, at room temperature by force
Power stirs 4h, and copper sulphate is completely dissolved, and obtains mixed solution；
S2：Mixed solution is moved into 24h is dried at 30 DEG C, obtain catalyst precursor powder；
S3：Catalyst precursor powder is warming up to 800 DEG C with 20 DEG C/min heating rate, 2h is then calcined, obtains
Solid particle；
S4：By solid particle in mortar repeatedly grinding until granularity be 120 mesh, obtain oxalic ester hydrogenation synthesizing of ethylene glycol
(stratiform Ce adulterates CuO/ZrO to catalyst2Oxalate hydrogenation catalyst), its pattern is as shown in Figure 2.
Example IV
The oxalic ester hydrogenation synthesizing of ethylene glycol catalyst that embodiment three is prepared, for oxalate hydrogenation synthesis second two
In alcohol, concrete application method comprises the following steps：
S101：Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst 1mL is filled in fixed-bed tube reactor, by catalyst
In volume space velocity 4000h-1, normal pressure H2250 DEG C are warming up to 10 DEG C/min under atmosphere, reduces 4h at this temperature, is had
There is the Cu base catalyst of certain activity；
S102：It is 260 DEG C, pressure 1.2MPa to adjust reaction temperature, and the liquid air speed of oxalic acid ester solution is 4.5h-1, will
Oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, with being catalyzed with certain active Cu bases
Agent carries out hydrogenation reaction, generates ethylene glycol；Wherein, H2Mol ratio with oxalate is 120:1.
As a result：Under the above-described reaction conditions, the conversion ratio of oxalate is 52.1%, and the selectivity of ethylene glycol is 55.6%,
The selectivity of ethyl glycolate is 37.1%, and the selectivity of ethanol is 7.3%；Catalyst stabilization runs 240h.
Embodiment five
The present embodiment provides a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, comprises the following steps：
S1：10.54g copper nitrates, 0.94g neodymium nitrates and 21.42g zirconium sulfates are added into acetic acid solution, at room temperature
Strong stirring 2h, copper nitrate are completely dissolved, and obtain mixed solution；
S2：Mixed solution is moved into 12h is dried at 80 DEG C, obtain catalyst precursor powder；
S3：Catalyst precursor powder is warming up to 600 DEG C with 12 DEG C/min heating rate, 3h is then calcined, obtains
Solid particle；
S4：By solid particle in mortar repeatedly grinding until granularity be 80 mesh, obtain oxalic ester hydrogenation synthesizing of ethylene glycol
(stratiform Nd adulterates CuO/ZrO to catalyst2Oxalate hydrogenation catalyst), its pattern is as shown in Figure 3.
Embodiment six
The oxalic ester hydrogenation synthesizing of ethylene glycol catalyst that embodiment five is prepared, for oxalate hydrogenation synthesis second two
In alcohol, concrete application method comprises the following steps：
S101：Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst 1mL is filled in fixed-bed tube reactor, by catalyst
In volume space velocity 3200h-1, 0.2MPa H2270 DEG C are warming up to 5 DEG C/min under atmosphere, reduces 3h at this temperature, is had
There is the Cu base catalyst of certain activity；
S102：It is 230 DEG C, pressure 1.8MPa to adjust reaction temperature, and the liquid air speed of oxalic acid ester solution is 2.8h-1, will
Oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, with being catalyzed with certain active Cu bases
Agent carries out hydrogenation reaction, generates ethylene glycol；Wherein, H2Mol ratio with oxalate is 50:1.
As a result：Under the above-described reaction conditions, the conversion ratio of oxalate is 88.6%, and the selectivity of ethylene glycol is 89.2%,
The selectivity of ethyl glycolate is 14.9%, and the selectivity of ethanol is 5.9%；Catalyst stabilization runs 240h.
Embodiment seven
The present embodiment provides a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, comprises the following steps：
S1：13.21g copper acetates, 0.31g praseodymium nitrates and 19.19g zirconium nitrates are added into acetic acid solution, at room temperature
Strong stirring 3h, copper acetate are completely dissolved, and obtain mixed solution；
S2：Mixed solution is moved into 10h is dried at 70 DEG C, obtain catalyst precursor powder；
S3：Catalyst precursor powder is warming up to 600 DEG C with 5 DEG C/min heating rate, then calcines 2h, consolidate
Body particle；
S4：By solid particle in mortar repeatedly grinding until granularity be 80 mesh, obtain oxalic ester hydrogenation synthesizing of ethylene glycol
(stratiform Pr adulterates CuO/ZrO to catalyst2Oxalate hydrogenation catalyst), its pattern is as shown in Figure 4.
Embodiment eight
The oxalic ester hydrogenation synthesizing of ethylene glycol catalyst that embodiment seven is prepared, for oxalate hydrogenation synthesis second two
In alcohol, concrete application method comprises the following steps：
S101：Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst 1mL is filled in fixed-bed tube reactor, by catalyst
In volume space velocity 50h-1, 0.4MPa H2160 DEG C are warming up to 2 DEG C/min under atmosphere, reduces 4h at this temperature, is had
The Cu base catalyst of certain activity；
S102：It is 180 DEG C, pressure 2.2MPa to adjust reaction temperature, and the liquid air speed of oxalic acid ester solution is 1.8h-1, will
Oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, with being catalyzed with certain active Cu bases
Agent carries out hydrogenation reaction, generates ethylene glycol；Wherein, H2Mol ratio with oxalate is 10:1.
As a result：Under the above-described reaction conditions, the conversion ratio of oxalate is 34.1%, and the selectivity of ethylene glycol is 35.7%,
The selectivity of ethyl glycolate is 61.3%, and the selectivity of ethanol is 3.0%；Catalyst stabilization runs 240h.
Embodiment nine
The present embodiment provides a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, comprises the following steps：
S1：16.99g copper acetates, 0.94g praseodymium nitrates and 14.02g acetic acid zirconiums are added into acetic acid solution, at room temperature
Strong stirring 4h, copper acetate are completely dissolved, and obtain mixed solution；
S2：Mixed solution is moved into 16h is dried at 60 DEG C, obtain catalyst precursor powder；
S3：Catalyst precursor powder is warming up to 500 DEG C with 1 DEG C/min heating rate, then calcines 3h, consolidate
Body particle；
S4：By solid particle in mortar repeatedly grinding until granularity be 100 mesh, obtain oxalic ester hydrogenation synthesizing of ethylene glycol
(stratiform Pr adulterates CuO/ZrO to catalyst2Oxalate hydrogenation catalyst), its pattern is as shown in Figure 5.
Embodiment ten
The oxalic ester hydrogenation synthesizing of ethylene glycol catalyst that embodiment nine is prepared, for oxalate hydrogenation synthesis second two
In alcohol, concrete application method comprises the following steps：
S101：Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst 1mL is filled in fixed-bed tube reactor, by catalyst
In volume space velocity 1200h-1, 0.4MPa H2220 DEG C are warming up to 3 DEG C/min under atmosphere, reduces 6h at this temperature, is had
There is the Cu base catalyst of certain activity；
S102：It is 210 DEG C, pressure 2.6MPa to adjust reaction temperature, and the liquid air speed of oxalic acid ester solution is 1.0h-1, will
Oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, with being catalyzed with certain active Cu bases
Agent carries out hydrogenation reaction, generates ethylene glycol；Wherein, H2Mol ratio with oxalate is 60:1.
As a result：Under the above-described reaction conditions, the conversion ratio of oxalate is 99.7%, and the selectivity of ethylene glycol is 98.7%,
The selectivity of ethyl glycolate is 0.7%, and the selectivity of ethanol is 0.6%；Catalyst stabilization runs 240h.
Embodiment 11
The present embodiment provides a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, comprises the following steps：
S1：18.88g copper nitrates, 0.62g lanthanum nitrates and 12.25g zirconium nitrates are added into acetic acid solution, at room temperature
Strong stirring 4h, copper nitrate are completely dissolved, and obtain mixed solution；
S2：Mixed solution is moved into 6h is dried at 120 DEG C, obtain catalyst precursor powder；
S3：Catalyst precursor powder is warming up to 550 DEG C with 1 DEG C/min heating rate, then calcines 2h, consolidate
Body particle；
S4：By solid particle in mortar repeatedly grinding until granularity be 80 mesh, obtain oxalic ester hydrogenation synthesizing of ethylene glycol
(stratiform La adulterates CuO/ZrO to catalyst2Oxalate hydrogenation catalyst), its pattern is as shown in Figure 6.
Embodiment 12
The oxalic ester hydrogenation synthesizing of ethylene glycol catalyst that embodiment 11 is prepared, for oxalate hydrogenation synthesis second
In glycol, concrete application method comprises the following steps：
S101：Oxalic ester hydrogenation synthesizing of ethylene glycol catalyst 1mL is filled in fixed-bed tube reactor, by catalyst
In volume space velocity 1600h-1, normal pressure H2230 DEG C are warming up to 2 DEG C/min under atmosphere, reduces 4h at this temperature, is had
The Cu base catalyst of certain activity；
S102：It is 220 DEG C, pressure 2.4MPa to adjust reaction temperature, and the liquid air speed of oxalic acid ester solution is 2.0h-1, will
Oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, with being catalyzed with certain active Cu bases
Agent carries out hydrogenation reaction, generates ethylene glycol；Wherein, H2Mol ratio with oxalate is 80:1.
As a result：Under the above-described reaction conditions, the conversion ratio of oxalate is 99.4%, and the selectivity of ethylene glycol is 97.2%,
The selectivity of ethyl glycolate is 1.7%, and the selectivity of ethanol is 1.1%；Catalyst stabilization runs 240h.
It should be noted that unless otherwise indicated, technical term or scientific terminology used in this application should be this hair
The ordinary meaning that bright one of ordinary skill in the art are understood.Unless specifically stated otherwise, otherwise illustrate in these embodiments
Part and relative step, numerical expression and the numerical value of step are not limit the scope of the invention.It is illustrated and described herein
In all examples, unless otherwise prescribed, any occurrence should be construed as merely exemplary, not as limitation, because
This, other examples of exemplary embodiment can have different values.
In the description of the invention, it is to be understood that term " first ", " second " are only used for describing purpose, and can not
It is interpreted as indicating or implies relative importance or imply the quantity of the technical characteristic indicated by indicating.Thus, define " the
One ", one or more this feature can be expressed or be implicitly included to the feature of " second ".In the description of the invention,
" multiple " are meant that two or more, unless otherwise specifically defined.
Finally it should be noted that：Various embodiments above is merely illustrative of the technical solution of the present invention, rather than its limitations；To the greatest extent
The present invention is described in detail with reference to foregoing embodiments for pipe, it will be understood by those within the art that：Its according to
The technical scheme described in foregoing embodiments can so be modified, either which part or all technical characteristic are entered
Row equivalent substitution；And these modifications or replacement, the essence of appropriate technical solution is departed from various embodiments of the present invention technology
The scope of scheme, it all should cover among protection scope of the present invention.
Claims (10)
1. a kind of preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst, it is characterised in that comprise the following steps：
S1：Soluble copper salt, soluble rare earth metal salt and soluble zirconates are added into acetic acid solution, stirred to metal salt
It is completely dissolved, obtains mixed solution；
S2：The mixed solution is dried, obtains catalyst precursor powder；
S3：The catalyst precursor powder is calcined, obtains solid particle；
S4：The solid particle is ground, obtains the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst.
2. the preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst according to claim 1, it is characterised in that：
In step S1, the copper in the soluble copper salt, the rare earth metal in the soluble rare earth metal salt and described solvable
The atomic ratio of zirconium in property zirconates is (54.3~25.2):1:(543~5.2).
3. the preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst according to claim 1, it is characterised in that：
In step S1, the soluble copper salt includes the one or more in copper nitrate, copper sulphate, copper carbonate and copper acetate；Institute
Stating soluble zirconates includes the one or more in zirconium nitrate, zirconium sulfate, zirconium carbonate and acetic acid zirconium；The soluble rare earth metal
Salt include lanthanum nitrate, lanthanum sulfate, lanthanum carbonate, lanthanum acetate, cerous nitrate, cerous sulfate, cerous carbonate, cerous acetate, neodymium nitrate, Dineodymium trisulfate,
One or more in neodymium carbonate, acetic acid neodymium, praseodymium nitrate, praseodymium sulfate, praseodymium carbonate and praseodymium acetate.
4. the preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst according to claim 1, it is characterised in that：
In step S2, the temperature of the drying is 30~150 DEG C, and the time of the drying is 2~24h.
5. the preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst according to claim 1, it is characterised in that：
In step S3, the calcining specifically includes：By the catalyst precursor powder with 1~20 DEG C/min heating rate liter
Then temperature calcines 1~10h to 400~800 DEG C；
In step S4, the grinding specifically includes：The solid particle is ground to granularity to 20~120 repeatedly in mortar
Mesh.
6. the preparation method of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst according to claim 1, it is characterised in that：
In step S4, before the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst is obtained after the grinding, include the step of shaping
Suddenly：The product that the grinding obtains is molded, the method for the shaping is selected from rotational forming, extruded moulding and compression molding
One or more.
7. the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst that the method described in claim any one of 1-6 is prepared.
8. the oxalic ester hydrogenation synthesizing of ethylene glycol catalyst described in claim 7 is in using oxalic ester hydrogenation synthesizing of ethylene glycol
Using.
9. application according to claim 8, it is characterised in that the method for the application comprises the following steps：
S101：The oxalic ester hydrogenation synthesizing of ethylene glycol catalyst is put into fixed bed reactors, carried out in pure hydrogen former
Position reduction, obtain the Cu base catalyst with certain activity；
S102：By oxalate vaporizer into gas, then with H2It is mixed into fixed bed reactors, has necessarily with described
The Cu bases catalyst of activity carries out hydrogenation reaction, generates ethylene glycol.
10. application according to claim 9, it is characterised in that：
In step S101, the reduction process specifically includes：The pressure of regulation reduction is 0~0.5MPa, adjusts H2Volume space velocity is
200~4000h-1, 160~300 DEG C then are warming up to 1~10 DEG C/min heating rate, restores 1~6h；
In step S102, reaction temperature is 180~260 DEG C, and pressure is 1.2~2.8MPa；The liquid-containing air of the oxalic acid ester solution
Speed is 0.2~8.0h-1, the H2Mol ratio with oxalate is (10~150):1.
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