CN106582652A - Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof - Google Patents
Catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, preparation method and applications thereof Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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Abstract
The present invention relates to a catalyst for ethylene glycol synthesis through gas phase hydrogenation of dimethyl oxalate, a preparation method and applications thereof. The catalyst comprises CuO, a metal auxiliary agent oxide and silica, wherein the Cu element accounts for 10-50% of the total weight of the catalyst, and the metal auxiliary agent element accounts for 1-10% of the total weight of the catalyst. The invention further discloses the preparation method of the catalyst. According to the present invention, a soluble copper salt and a metal auxiliary agent soluble salt are used and are added with ammonia water to form an ammonia complex aqueous solution, aging-ammonia evaporation and co-precipitating are performed, and the obtained material and silica form the gel so as to form the stable chemical structure, such that the stability of the catalyst is substantially improved; during the preparation process, the organic modifier is added so as to effectively improve the pore structure and the specific surface area of the catalyst, and improve the activity of the catalyst and the ethylene glycol selectivity; and with the application of the catalyst in the dimethyl oxalate hydrogenation reaction, the service life is more than one year, the average conversion rate of dimethyl oxalate is more than 99.9%, and the ethylene glycol selectivity is more than 95%.
Description
Technical field
The present invention relates to a kind of catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol and preparation method and application, belongs to
Catalyst technical field.
Background technology
Ethylene glycol also known as glycol, are a kind of no color or smell, pleasantly sweet liquid, are a kind of important basic petrochemical raw materials.
Can be used to manufacture polyester fiber, plastics, rubber, antifreezing agent, unsaturated polyester resin, nonionic surfactant, ethanol
Amine and explosive etc., it can also be used to prepare low-freezing coolant, as solvent etc., purposes is quite varied.
At present, the main method of domestic and international commercial synthesis ethylene glycol is traditional petroleum path, i.e., oxidation of ethylene generates oxirane
(EO), then ethylene oxide hydration generates ethylene glycol.The production method has unsurmountable shortcoming, is mainly manifested in work
Skill long flow path, equipment are more, energy consumption, and ethylene glycol relative selectivity is poor.Due to China's oil resource-constrained, oil externally according to
Degree of depositing is high, at present, it has also become global first big oil importers, while coal resources but relative abundance.China's economic is in
Stage of Strategic Transformation, ecological, environmental protection are more and more stronger to the constraint of coal test, cause history in recent years at coal price
Status, coal production capacity are seriously superfluous, in order to solve this problem, it is necessary to the New Coal Chemical of development environment friendly, widen coal
Charcoal utilizes development.Therefore, develop Non oil-based route to carry out synthesizing glycol and seem extremely meaningful in the phase of current economic transition,
Particularly with coal as raw material, synthesizing glycol, this process route, this route technological process are simple, and energy consumption is little, ethylene glycol choosing
Selecting property is high, and energy utilization rate is high, environmental protection.
The method of synthesis gas preparing ethylene glycol has oxalic acid ester process, methanol dimerization method, formaldehyde electrification hydrogenation dimerization method and formaldehyde hydroformylation
Method.Wherein, CO catalytic couplings synthesis of oxalate, then Jing oxalic ester hydrogenation synthesizing of ethylene glycol, is current C1 chemical research
Popular direction.The method reaction condition is gentle, low cost, and product purity is high.Lot of domestic and international company and research institution, such as shut out
Company of nation, Xue Fulong companies, ARCO companies, the emerging product in space portion, UCC companies of the U.S., one chemical industry reality of domestic University Of Tianjin carbon
Test room, Fujian Inst. of Matter Structure, Chinese Academy of Sciences, East China University of Science, Fudan University etc. all to study this route,
Wherein, exploitation, with high selectivity, the Hydrogenation of Dimethyl Oxalate catalyst of high stability, is difficult point generally acknowledged in the industry.
It is related to catalyst of oxalic ester hydrogenation synthesizing of ethylene glycol and preparation method thereof patent report more.Earlier patents are mainly concentrated
Abroad, wherein Japan at most, mainly Ube company：As Japan Patent 5323011 and 5542971 proposes grass first
Acid esters gas phase hydrogenation preparing ethylene glycol this route, clear 57-122938, clear 57-122939, clear 57-122940 and clear 57-1870432
Etc. describing different method for preparing catalyst；United States Patent (USP) 4585890,4440873 etc. discloses the preparation of cuprammonium silica gel method
Copper-based catalysts；European patent 0060787 reports a kind of copper Si catalyst containing Cr, and ARCO companies of the U.S. employ
Cu-Cr catalyst；The country is that Chinese Academy of Sciences's Fujian thing structure also develops Cu-Cr catalyst in the nineties earliest, completes oxalic acid
The 200mL moulds examination research work of diethylester hydrogenation preparing ethylene glycol, afterwards, domestic Hydrogenation of Dimethyl Oxalate patent is very more, such as
CN200910048025.8, CN200910138261.9, CN201010191578.1 etc..By analyzing and summarizing above-mentioned patent,
It was found that the subject matter that oxalate hydrogenation catalyst is present is：Reaction hydrogen ester it is higher, liquid hourly space velocity (LHSV) is relatively low, selectivity of product compared with
It is low, the shortcomings of catalyst life is short.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of dimethyl oxalate. gas phase hydrogenation synthesizing glycol
Catalyst and preparation method and application.Prepared using precipitate gel ammonia still process method, it is solvable using copper soluble-salt and metal promoter
Property salt add ammonia to form ammino-complex aqueous solution, is combined with silicon dioxide, ammonia still process co-precipitation, the stable chemical constitution of formation,
Improve the stability of catalyst, while add modifying agent under catalyst gel state, be effectively improved catalyst pore structure and
Specific surface area, improves the activity of the catalyst, and the selectivity of ethylene glycol.The catalyst is applied to Hydrogenation of Dimethyl Oxalate
In reaction, service life reaches more than 1 year, and dimethyl oxalate. average conversion reaches more than 99.9%, and glycol selectivity reaches
To more than 95%, the needs of industrialized production can be met.
The present invention is achieved by the following technical solutions：
A kind of catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol, including active component and carrier, the active component
For CuO and the oxide of metal promoter, the metal promoter is selected from one or more in Ni, Zn, Co and Zr, described
Carrier is silicon dioxide, and Cu elements account for the 10～50% of total catalyst weight, and metal promoter element accounts for total catalyst weight
1～10%.
It is that catalyst removes the remaining amount of active component that the carrier accounts for the content of total catalyst weight.
Preferably, Cu elements account for the 20～40% of total catalyst weight, and metal promoter element accounts for the 1～5% of total catalyst weight.
Cu elements can account for 10～20%, 20～30%, 30～40% or the 40～50% of total catalyst weight.
Metal promoter element can account for 1～3%, 3～5% or the 5～10% of total catalyst weight.
Preferably, the silicon dioxide is Ludox or hydrophilic white carbon.It is furthermore preferred that the silicon dioxide is hydrophilic
White carbon, specific surface area are 100～500m2/g。
Preferably, the specific surface area of the catalyst is 200～500m2/ g, pore volume be 0.3～1.8mL/g, aperture be 1.0～
20.0nm。
The present invention further discloses a kind of preparation method of the catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol,
Comprise the following steps：
(1) mixed aqueous solution of copper soluble-salt and metal promoter soluble-salt is prepared, ammonia is added, ammino-complex is formed
Aqueous solution；
(2) be uniformly mixed in the ammino-complex aqueous solution for adding step (1) to prepare in carrier, aging acquisition catalyst
Mother solution；
(3) ammonia still process reaction will be carried out under the conditions of the catalyst mother solution water-bath obtained by step (2), reaction is catalyzed after terminating
Agent gel；
(4) catalyst gel obtained by step (3) is filtered, washing obtains catalyst cake；
(5) stand after stirring after adding organic modifiers in the catalyst cake obtained by step (4), be dried and roast
Burn, that is, the catalyst of the dimethyl oxalate. gas phase hydrogenation synthesizing glycol is obtained.
Preferably, in step (1), the copper soluble-salt is selected from one or more in copper nitrate, copper sulfate and Schweinfurt green；
The metal promoter soluble-salt is selected from one or more in nitrate, sulfate and the acetate of metal promoter.
Preferably, in step (1), the pH value of the ammino-complex aqueous solution is 10.5～12.5.It is furthermore preferred that step (1)
In, the pH value of the ammino-complex aqueous solution is 11.0～12.0.Less than 10.5, it is thinner to easily cause catalyst particle size,
Washing is difficult, and makes catalyst life shorten.
In step (1), the pH value of the ammino-complex aqueous solution can be 10.5～11,11～11.5,11.5～12 or 12～12.5.
Preferably, in step (2), the aging time is 4～12 hours.
In step (2), the aging time can be 4～8 hours or 8～12 hours.
Preferably, in step (2), the carrier is Ludox, and in Ludox, dioxide-containing silica is 10～25wt%.
Preferably, in step (2), the carrier is hydrophilic white carbon, and specific surface area is 100～500m2/g.More preferably
, in step (2), specific surface area is 200～400m2/g。
Preferably, in step (3), the temperature of the water-bath is 50～100 DEG C.It is furthermore preferred that in step (3), it is described
The temperature of water-bath is 70～95 DEG C.
In step (3), the temperature of the water-bath can be 50～85 DEG C or 85～100 DEG C.
Preferably, in step (3), the end-condition of the ammonia still process reaction is：PH value is 6～8, on the one hand ensure that activity
Component all can be precipitated, and wash filtrate on the other hand can be made to keep more limpid, waste water environmental protection treatment difficulty is reduced.More
Preferably, in step (3), the end-condition of the ammonia still process reaction is：PH value is 6～7.
In step (3), the end-condition of the ammonia still process reaction is：PH value can be 6～6.5,6.5～7.5 or 7.5～8.
Preferably, in step (5), the organic modifiers are selected from ethanol, ethylene glycol or Polyethylene Glycol.
It is furthermore preferred that the organic modifiers are Polyethylene Glycol.It is furthermore preferred that the degree of polymerization of the organic modifiers is
400～1800.
The degree of polymerization of the organic modifiers can be 400～1000 or 1000～1800.
Preferably, in step (5), the organic modifiers addition is 1～10% of vehicle weight in the catalyst.More
Preferably, the organic modifiers addition is 2～5% of vehicle weight in the catalyst.
In step (5), the organic modifiers addition can be 1～5% or 5～10% of vehicle weight in the catalyst.
Preferably, in step (5), after stirring, stand 1～4 hour.It is furthermore preferred that it is little that 2～3 are stood after stirring
When.
In step (5), 1～3 hour can be stood after stirring or 3～4 hours.
Preferably, in step (5), dry temperature is 80～120 DEG C, and the dry time is 8～12 hours.
In step (5), dry temperature can be 80～95 DEG C or 95～120 DEG C.
In step (5), the dry time is 8～9 hours or 9～12 hours.
Preferably, in step (5), the catalyst solid after the drying is complete, aqueous 2～30wt%, more preferably 5～20wt%.
Preferably, in step (5), the temperature of roasting is 300～750 DEG C, and the time of roasting is 3～10 hours.It is furthermore preferred that
In step (5), the sintering temperature is 300～700 DEG C, preferably 300～600 DEG C；Roasting time 4～8 hours, preferably 4～6
Hour.
In step (5), the temperature of roasting can be 300～500 DEG C or 500～750 DEG C.
In step (5), the time of roasting can be 3～5 hours or 5～10 hours.
Above-mentioned catalyst provided in the present invention can be used for the reaction of dimethyl oxalate. gas phase hydrogenation synthesizing glycol.
Preferably, the catalyst is reduced with hydrogen or hydrogen nitrogen mixed gas using front, and reduction temperature is 120～300 DEG C, also
3～12 hours former time.
Reduction temperature can be 120～210 DEG C, 210～250 DEG C or 250～300 DEG C.
Preferably, the catalyst is applied to dimethyl oxalate. gas phase hydrogenation synthesizing glycol, and hydrogenation technique parameter is：With grass
Dimethyl phthalate is reaction raw materials, 165～250 DEG C of controlling reaction temperature, 1.0～4.0MPa of reaction pressure, dimethyl oxalate. liquid
When air speed be 0.4～2.0g/mLcat.h, the molecular proportion of hydrogen and oxalate is 40～200: 1.
In hydrogenation technique parameter, reaction temperature can be 165～170 DEG C, 170～190 DEG C or 190～250 DEG C, and reaction pressure can be
1.0～3.0MPa or 3.0～4.0MPa, dimethyl oxalate. liquid hourly space velocity (LHSV) can for 0.4～0.7g/mLcat.h or 0.7～
2.0g/mLcat.h, hydrogen can be 40～60: 1,60～80: 1,80～100: 1 or 100～200 with the molecular proportion of oxalate:
1。
The present invention forms ammonia complexing together with active ingredient copper by one or more metal promoter in Ni, Zn, Co, Zr
Thing solution, during ammonia still process, removes the free ammonia in catalyst mother solution, and copper occurs co-precipitation, catalyst with metal promoter
Mother solution is changed into collosol and gel state, and stable chemical constitution is formed together with carrier silicas, improve high temperature resistance reunite and
Caking power, on the premise of catalyst activity is ensured, improves the life-span of catalyst.In catalyst gel state, add
Plus organic modifiers, suitable catalyst duct is formed, improves catalyst pore structure and specific surface area, so as to further improve
The activity of catalyst, and glycol selectivity.Catalyst of the present invention in 170～230 DEG C of reaction temperature, reaction pressure 2.0～
Under 4.0MPa, Hydrogenation of Dimethyl Oxalate reaction is carried out, ethylene glycol space-time yield is high, and raw material dimethyl oxalate. (DMO) is average
Conversion ratio reaches more than 99.9%, is close to 100%, and target product glycol selectivity reaches more than 95%, and by-product is especially
The impurity content of impact ethylene glycol performance is low, and reaction bed temperature is stable, and catalyst service life was up to more than 1 year.Test
Show, catalyst obtained in the preparation method of the present invention has very high reaction activity, second two in oxalate gas phase hydrogenation reaction
Alcohol selectivity is high, life-span length.
Specific embodiment
Technical scheme is illustrated below by way of specific instantiation.It should be understood that one or more sides that the present invention is mentioned
Method step is not repelled
May be inserted into additive method step；It should also be understood that these embodiments are merely to illustrate the present invention rather than limit the model of the present invention
Enclose.And, unless otherwise stated, the numbering of various method steps only differentiates the convenient tool of various method steps, rather than to limit
The ordering of various method steps limits enforceable scope of the invention, and its relativeness is altered or modified, without substantive change
In the case of more technology contents, when being also considered as enforceable category of the invention.
Embodiment 1
Prepare the catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol, oxygen of the active component for CuO and Ni metal promoters
Compound, carrier is silicon dioxide, and Cu elements account for 20wt%, Ni metal promoter element of total catalyst weight and account for overall catalyst weight
The 3wt% of amount, balance of carrier silicas, preparation method are as follows：
Weigh copper nitrate (Cu (NO3)2·3H2O) 30g, nickel nitrate (Ni (NO3)2·6H2O) 5.9g, adds 400ml to go
Ion water dissolution；Deca strong aqua ammonia, forms ammino-complex aqueous solution, control ph about 11.5；White carbon 28.25g is added,
Mechanical agitation is aging 8 hours；Rising system bath temperature to 85 DEG C, until pH stops for 6.5, urge by ammonia still process 2～3 hours
Agent mother solution becomes gel-like state；Filter, washing obtains catalyst cake；Add organic modifiers in catalyst cake to gather
Ethylene glycol 1.5g (5wt% of white carbon addition), the degree of polymerization 1000 are stirred, and are placed 3 hours, are put into baking
In case, 95 DEG C of dryings 9 hours, are positioned over Muffle kiln roasting, 500 DEG C of roastings 5 hours, obtain dimethyl oxalate. gas phase
The catalyst of hydrogenation synthesizing of ethylene glycol.BET test results such as table 1.
The use of procatalyst hydrogen volume content is the hydrogen of 50v%, nitrogen mixture reduction, reduction temperature is 210 DEG C.
Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, with dimethyl oxalate. as reaction raw materials, controlling reaction temperature
190 DEG C, reaction pressure 3.0MPa, dimethyl oxalate. liquid hourly space velocity (LHSV) are the molecule of 0.7g/mLcat.h, hydrogen and dimethyl oxalate.
Than for 60.Evaluation result is shown in Table 2.
Embodiment 2
Prepare that dimethyl oxalate. gas phase hydrogenation is glycol catalyst synthesized, oxidation of the active component for CuO and Ni metal promoters
Thing, carrier is silicon dioxide, and Cu elements account for 30wt%, Ni metal promoter element of total catalyst weight and account for total catalyst weight
3wt%, balance of carrier silicas, preparation method are as follows：
Weigh copper nitrate (Cu (NO3)2·3H2O) 50g, nickel nitrate (Ni (NO3)2·6H2O) 6.5g, adds 400ml to go
Ion water dissolution；Deca strong aqua ammonia, is made into ammino-complex solution, control ph about 12.5；Add white carbon 26g, machine
Tool stirring is aging 8 hours；To 85 DEG C, ammonia still process 2～3 hours, until pH stops for 6.0, is catalyzed rising system bath temperature
Agent mother solution becomes gel-like state；Filter, washing obtains catalyst cake；Add the poly- second of organic modifiers in catalyst cake
Glycol 1.3g (5wt% of white carbon addition), the degree of polymerization 400 are stirred, and are placed 3 hours, are put in baking oven,
95 DEG C of dryings, 9 hours, are positioned over Muffle kiln roasting, 500 DEG C of roastings 5 hours, obtain the conjunction of dimethyl oxalate. gas phase hydrogenation
Into the catalyst of ethylene glycol.BET test results such as table 1.
The use of procatalyst hydrogen volume content is the hydrogen of 50v%, nitrogen mixture reduction, reduction temperature is 250 DEG C.
Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, with dimethyl oxalate. as reaction raw materials, controlling reaction temperature
190 DEG C, reaction pressure 3.0MPa, dimethyl oxalate. liquid hourly space velocity (LHSV) are the molecule of 0.7g/mLcat.h, hydrogen and dimethyl oxalate.
Than for 80.Evaluation result is shown in Table 2.
Embodiment 3
Prepare that dimethyl oxalate. gas phase hydrogenation is glycol catalyst synthesized, oxidation of the active component for CuO and Ni metal promoters
Thing, carrier is silicon dioxide, and Cu elements account for 40wt%, Ni metal promoter element of total catalyst weight and account for total catalyst weight
3wt%, balance of carrier silicas, preparation method are as follows：
Weigh copper nitrate (Cu (NO3)2·3H2O) 70g, nickel nitrate (Ni (NO3)2·6H2O) 6.9g, adds 400ml to go
Ion water dissolution；Deca strong aqua ammonia, is made into ammino-complex solution, control ph about 11.0；Add white carbon 21g, machine
Tool stirring is aging 8 hours；To 85 DEG C, ammonia still process 2～3 hours, until pH stops for 7.5, is catalyzed rising system bath temperature
Agent mother solution becomes gel-like state；Filter, washing obtains catalyst cake；Add the poly- second of organic modifiers in catalyst cake
Glycol 1.1g (5wt% of white carbon addition), the degree of polymerization 1800 are stirred, and are placed 3 hours, are put in baking oven,
95 DEG C of dryings, 9 hours, are positioned over Muffle kiln roasting, 500 DEG C of roastings 5 hours, obtain the conjunction of dimethyl oxalate. gas phase hydrogenation
Into the catalyst of ethylene glycol.BET test results such as table 1.
The use of procatalyst hydrogen volume content is the hydrogen of 50v%, nitrogen mixture reduction, reduction temperature is 300 DEG C.
Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, with dimethyl oxalate. as reaction raw materials, controlling reaction temperature
190 DEG C, reaction pressure 3.0MPa, dimethyl oxalate. liquid hourly space velocity (LHSV) are the molecule of 0.7g/mLcat.h, hydrogen and dimethyl oxalate.
Than for 100.Evaluation result is shown in Table 2.
Embodiment 4
Prepare dimethyl oxalate. gas phase hydrogenation glycol catalyst synthesized, ammonia still process terminal pH to 8 stop, preparation method step and
Other parameters reference implementation example 1.
The use of procatalyst hydrogen volume content is the hydrogen of 50v%, nitrogen mixture reduction, reduction temperature is 300 DEG C.
Evaluated on the micro-reactor of 10 milliliters of loaded catalysts, with dimethyl oxalate. as reaction raw materials, controlling reaction temperature
170 DEG C, reaction pressure 3.0MPa, dimethyl oxalate. liquid hourly space velocity (LHSV) are the molecule of 0.7g/mLcat.h, hydrogen and dimethyl oxalate.
Than for 100.Evaluation result is shown in Table 2.
Embodiment 5
Prepare that dimethyl oxalate. gas phase hydrogenation is glycol catalyst synthesized, oxidation of the active component for CuO and Ni metal promoters
Thing, carrier is silicon dioxide, and Cu elements account for 20wt%, Ni metal promoter element of total catalyst weight and account for total catalyst weight
5wt%, balance of carrier silicas, preparation method step and other parameter reference embodiments 1；Catalyst in-service evaluation
Condition is with embodiment 1.BET test results and evaluation result are shown in Table 2.
Embodiment 6
The catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol is prepared, metal promoter soluble-salt uses cobalt nitrate instead
(Co(NO3)2·6H2), O preparation method step and other parameter reference embodiments 1；Catalyst in-service evaluation condition is with enforcement
Example 1.BET test results and evaluation result are shown in Table 2.
Embodiment 7
The catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol is prepared, metal promoter soluble-salt uses zirconium nitrate instead
(Zr(NO3)4·5H2), O preparation method step and other parameter reference embodiments 2；Catalyst in-service evaluation condition is with enforcement
Example 2.BET test results and evaluation result are shown in Table 2.
Embodiment 8
The catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol is prepared, metal promoter soluble-salt uses zinc nitrate instead
(Zn(NO3)2·6H2), O preparation method step and other parameter reference embodiments 3；Catalyst in-service evaluation condition is with enforcement
Example 3.BET test results and evaluation result are shown in Table 2.
Embodiment 9
The catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol is prepared, white carbon is replaced using Ludox, Ludox is weighed
100g, thickness of silica gel are 25wt%, preparation method step and other parameter reference embodiments 1；Catalyst in-service evaluation condition
With embodiment 1.BET test results and evaluation result are shown in Table 2.
In embodiment 1-8, metallic salt can be replaced with sulfate and acetate, can reach identical effect.
Embodiment 10
Cu elements account for the 3wt% that 10wt%, Ni metal promoter element of total catalyst weight accounts for total catalyst weight, other systems
Standby process and parameter are obtained the catalyst of preparing ethylene glycol by using dimethyl oxalate plus hydrogen with embodiment 1.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Embodiment 11
Cu elements account for the 3wt% that 50wt%, Ni metal promoter element of total catalyst weight accounts for total catalyst weight, other systems
Standby process and parameter are obtained the catalyst of preparing ethylene glycol by using dimethyl oxalate plus hydrogen with embodiment 1.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Embodiment 12
Cu elements account for the 1wt% that 20wt%, Ni metal promoter element of total catalyst weight accounts for total catalyst weight, other systems
Standby process and parameter are obtained the catalyst of preparing ethylene glycol by using dimethyl oxalate plus hydrogen with embodiment 1.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Embodiment 13
Cu elements account for the 10wt% that 20wt%, Ni metal promoter element of total catalyst weight accounts for total catalyst weight, other systems
Standby process and parameter are obtained the catalyst of preparing ethylene glycol by using dimethyl oxalate plus hydrogen with embodiment 1.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Embodiment 14
Ammino-complex solution is prepared, it is 10.5 to control pH, and other preparation process and parameter are obtained oxalic acid diformazan with embodiment 1
The catalyst of ester through hydrogenation preparing ethylene glycol.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Embodiment 15
Addition organic modifiers ethylene glycol 5%, other preparation process and parameter are obtained prepared by dimethyl oxalate plus hydrogen with embodiment 1
The catalyst of ethylene glycol.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Embodiment 16
Addition organic modifiers Polyethylene Glycol 1%, the degree of polymerization 1000, other preparation process and parameter are obtained grass with embodiment 1
Dimethyl phthalate is hydrogenated with the catalyst of preparing ethylene glycol.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Embodiment 17
Addition organic modifiers Polyethylene Glycol 10%, the degree of polymerization 1000, other preparation process and parameter are obtained grass with embodiment 1
Dimethyl phthalate is hydrogenated with the catalyst of preparing ethylene glycol.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Comparative example 1
Metal promoter is not added with, other preparation process and parameter are obtained urging for preparing ethylene glycol by using dimethyl oxalate plus hydrogen with embodiment 1
Agent.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Comparative example 2
Organic modifiers are not added with, other preparation process and parameter are obtained preparing ethylene glycol by using dimethyl oxalate plus hydrogen with embodiment 1
Catalyst.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
Comparative example 3
Metal promoter and organic modifiers are not added with, other preparation process and parameter are obtained Hydrogenation of Dimethyl Oxalate with embodiment 1
The catalyst of preparing ethylene glycol.BET test results are shown in Table 1.
With embodiment 1, evaluation result is shown in Table 2 to the in-service evaluation condition of catalyst.
1 catalyst BET test results of table
2 evaluating catalyst result of table
| CDMO | SEG | SMG |
| % | % | % | |
| Embodiment 1 | 100 | 95.0 | 0.9 |
| Embodiment 2 | 100 | 96.8 | 0.7 |
| Embodiment 3 | 100 | 96.5 | 0.5 |
| Embodiment 4 | 100 | 95.5 | 0.9 |
| Embodiment 5 | 100 | 96.0 | 0.8 |
| Embodiment 6 | 99.9 | 95.0 | 0.7 |
| Embodiment 7 | 99.9 | 95.3 | 0.8 |
| Embodiment 8 | 100 | 96.0 | 0.5 |
| Embodiment 9 | 100 | 95.8 | 0.8 |
| Embodiment 10 | 99.9 | 93.5 | 0.9 |
| Embodiment 11 | 100 | 98.0 | 0.3 |
| Embodiment 12 | 100 | 94.8 | 0.85 |
| Embodiment 13 | 100 | 93.5 | 0.9 |
| Embodiment 14 | 99.9 | 93.0 | 1.2 |
| Embodiment 15 | 100 | 95.0 | 0.95 |
| Embodiment 16 | 100 | 94.0 | 1.3 |
| Embodiment 17 | 100 | 96.5 | 0.6 |
| Comparative example 1 | 99.9 | 95.4 | 1.4 |
| Comparative example 2 | 99.9 | 94.5 | 1.5 |
| Comparative example 3 | 100 | 94.0 | 1.9 |
Note：DMO is dimethyl oxalate., and EG is ethylene glycol, and MG is methyl glycollate；C represents conversion ratio, and S represents selection
Property.
Claims (12)
1. a kind of catalyst of dimethyl oxalate. gas phase hydrogenation synthesizing glycol, it is characterised in that including active component and carrier, institute
State active component for CuO and metal promoter oxide, the one kind of the metal promoter in Ni, Zn, Co and Zr or
Various, the carrier is silicon dioxide, and Cu elements account for the 10～50% of total catalyst weight, and metal promoter element accounts for catalyst
The 1～10% of gross weight.
2. catalyst as claimed in claim 1, it is characterised in that Cu elements account for the 20～40% of total catalyst weight, metal promoted
Agent element accounts for the 1～5% of total catalyst weight.
3. catalyst as claimed in claim 1, it is characterised in that the silicon dioxide is Ludox or hydrophilic white carbon.
4. catalyst as claimed in claim 1, it is characterised in that the specific surface area of the catalyst is 200～500m2/ g, hole
Hold for 0.3～1.8mL/g, aperture is 1.0～20.0nm.
5. a kind of preparation method of the catalyst as described in Claims 1-4 is arbitrary, comprises the following steps：
(1) mixed aqueous solution of copper soluble-salt and metal promoter soluble-salt is prepared, ammonia is added, ammino-complex is formed
Aqueous solution；
(2) be uniformly mixed in the ammino-complex aqueous solution for adding step (1) to prepare in carrier, aging acquisition catalyst
Mother solution；
(3) ammonia still process reaction will be carried out under the conditions of the catalyst mother solution water-bath obtained by step (2), reaction is catalyzed after terminating
Agent gel；
(4) catalyst gel obtained by step (3) is filtered, washing obtains catalyst cake；
(5) stand after stirring after adding organic modifiers in the catalyst cake obtained by step (4), be dried and roast
Burn, that is, the catalyst of the dimethyl oxalate. gas phase hydrogenation synthesizing glycol is obtained.
6. preparation method as claimed in claim 5, it is characterised in that in step (1), also including following characteristics in it is arbitrary
Item is multinomial：
1. the copper soluble-salt is selected from one or more in copper nitrate, copper sulfate and Schweinfurt green；The metal promoter solubility
Salt is selected from one or more in nitrate, sulfate and the acetate of metal promoter；
2. the pH value of the ammino-complex aqueous solution is 10.5～12.5.
7. preparation method as claimed in claim 5, it is characterised in that in step (2), also including following characteristics in it is arbitrary
Item is multinomial：
1. the aging time is 4～12 hours；
2. the carrier is Ludox, and in Ludox, dioxide-containing silica is 10～25wt%；
3. the carrier is hydrophilic white carbon, and specific surface area is 100～500m2/g。
8. preparation method as claimed in claim 5, it is characterised in that in step (3), also including following characteristics in it is arbitrary
Item is multinomial：
1. the temperature of the water-bath is 50～100 DEG C；
2. the end-condition of the ammonia still process reaction is：PH value is 6～8.
9. preparation method as claimed in claim 5, it is characterised in that in step (5), also including any one of following characteristics
Or it is multinomial：
1. the organic modifiers are selected from ethanol, ethylene glycol or Polyethylene Glycol；
2. the organic modifiers addition is 1～10% of vehicle weight in the catalyst；
3. 1～4 hour is stood after stirring；
4. dry temperature is 80～120 DEG C, and the dry time is 8～12 hours；
5. the temperature of roasting is 300～750 DEG C, and the time of roasting is 3～10 hours.
10. the catalyst as described in Claims 1-4 is arbitrary is used for the reaction of dimethyl oxalate. gas phase hydrogenation synthesizing glycol.
11. purposes as claimed in claim 10, it is characterised in that the catalyst using front, with hydrogen or hydrogen nitrogen mixed gas also
Original, reduction temperature are 120～300 DEG C, 3～12 hours recovery times.
12. purposes as claimed in claim 10, it is characterised in that the catalyst is applied to the synthesis of dimethyl oxalate. gas phase hydrogenation
Ethylene glycol, hydrogenation technique parameter is：With dimethyl oxalate. as reaction raw materials, 165～250 DEG C of controlling reaction temperature, reaction pressure
1.0～4.0MPa of power, dimethyl oxalate. liquid hourly space velocity (LHSV) is 0.4～2.0g/mLcat.h, the molecular proportion of hydrogen and oxalate is 40～
200∶1。
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