CN109569619A - Carbon monoxide-olefin polymeric, Manufacturing approach and use - Google Patents
Carbon monoxide-olefin polymeric, Manufacturing approach and use Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/78—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 alkali- or alkaline earth metals
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/83—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 rare earths or actinides
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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
- B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—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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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The present invention relates to a kind of carbon monoxide-olefin polymerics, Manufacturing approach and use, mainly solve that the technical problem that activity and selectivity is low, stability is poor exists in the prior art.The carbon monoxide-olefin polymeric has chemical formula M-Cu-X/SiO2‑TiO2；Wherein, M is selected from least one of the group being made of the oxide of Mg, Ca, Sr and Ba；X is selected from least one of the group being made of the oxide of V, Cr, Zn, Fe, Ni, Co and Mn；Based on parts by weight, the content of M is 2-12 parts, and the content of Cu element is 10-40 parts, and the content of X is 2-20 parts, SiO2‑TiO2Content be 28-86 parts；SiO2‑TiO2In, TiO2Account for SiO2‑TiO2Weight ratio be 1-20%.The catalyst can be used in the industrial production of hydrogenation of oxalate for preparing ethylene glycol.
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymerics, Manufacturing approach and use.
Background technique
Ethylene glycol (abbreviation EG) is a kind of important basic petrochemical Organic Ingredients, can derive more than 100 kinds of changes from it
Product.Wherein, polyester (including polyester fiber, polyester bottles, polyester film etc.) is the major consumers field of China's ethylene glycol, is disappeared
Expense amount accounts for about the 90% of gross domestic consumption amount；In addition about 10% for antifreezing agent, binder, paint solvent, Everlube with
And surfactant etc..Industrial production ethylene glycol route is that naphtha pyrolysis produces ethylene at present, and ethylene produces epoxy second
Alkane (abbreviation EO), last ethylene oxide hydration obtain ethylene glycol.Under the economic environment that oil price remains high, people are increasingly
Recognize the finiteness of petroleum resources, various countries begin one's study one after another using coal and natural gas as primary raw materials and produce ethylene glycol.It closes
At gas preparing ethylene glycol route due to have raw material extensively, good economy performance, the more reasonable advantage of technique, gradually become Non oil-based route
The research hotspot of synthesizing glycol.Synthesis gas preparing ethylene glycol route is from synthesis gas by CO gas-phase catalytic coupling synthesis of oxalic acid
Ester, repeated hydrogenation prepare ethylene glycol.The dependence to petroleum resources is got rid of from raw material, actively complies with ethylene glycol production technology development tide
It flows, for the country more especially for such a coal in China, oil is few, exploitation coal process route has increasingly important meaning
Justice.
The key technology of coal based synthetic gas preparing ethylene glycol first is that the exploitation of oxalic ester hydrogenation synthesizing of ethylene glycol catalyst.Beauty
ARCO company, state proposes copper chromium-based catalysts with preferable hydrogenation activity and selectivity in patent US54112245, uses
It is supported on Al2O3、SiO2Or copper-chromium-based catalysts on bead, 200-230 DEG C of reaction temperature, but ethylene glycol yield only has
11.7-18.9%.In order to improve the selectivity and yield of reaction, correlative study person starts to develop the catalysis of oxalate gas phase hydrogenation
Agent, EP46983 propose the route of oxalate gas phase hydrogenation preparing ethylene glycol on copper chromium-based catalysts.
It is (clear 57-122939, clear 57-122946, clear that Ube Industries Ltd. in the eighties in last century discloses a collection of patent
57-123127 etc.), they have investigated carrier (Al to the catalyst based on copper2O3、SiO2、La2O3Deng), auxiliary agent (K, Zn,
Ag, Mo, Ba etc.), the influence to catalyst activity and selectivity such as preparation method.By adding in the catalyst based on copper
Enter the selectivity that auxiliary agent changes reaction, Zn, which is added, can be improved the selectivity of ethylene glycol, and the choosing that Ag improves methyl glycollate is added
Selecting property changes reaction condition (temperature, pressure, air speed, hydrogen ester ratio etc.) adjustable product distribution under same catalyst, from
And obtain the product based on methyl glycollate and ethylene glycol.
Domestic related research institutes study oxalate hydrogenation catalyst since the eighties in last century.Document (" work
Industry catalysis ", 1996,4:24-29) use Cu-Cr catalyst carried out grass under conditions of 208-230 DEG C, 2.5-3.0MPa
Diethyl phthalate adds the mould of hydrogen to try research, and reaction result is diethy-aceto oxalate conversion ratio 99.8%, ethylene glycol average selectivity
95.3%, catalyst can be run 1134 hours.In recent years, domestic like a raging fire to the research of oxalate hydrogenation catalyst.Document
CN101524646A is proposed with Al2O3For carrier, one or more of Zn, Mn, Mg, Cr are the copper-based catalysts of auxiliary agent, reaction
Pressure is 0.1-1.0MPa, and reaction temperature is 145-220 DEG C, and oxalate liquid hourly space velocity (LHSV) is 0.1-0.6h-1, oxalic acid ester conversion rate is big
In 99%, glycol selectivity is greater than 90%.Document CN101342489A discloses a kind of copper silicon systems hydrogenation catalyst containing auxiliary agent
Agent, auxiliary agent be selected from one of alkaline-earth metal, transition metal element or thulium or more than one, it is anti-in 3.0MPa
Answer pressure, under the process conditions of polybasic ester liquid hourly space velocity (LHSV) 0.7h-1,99% or more feed stock conversion, glycol selectivity 95%
More than.Document CN101138725A discloses a kind of catalyst and preparation method thereof of oxalate synthesizing glycol, with copper
For active component, Zn-ef ficiency is auxiliary agent, is prepared using infusion process, the catalyst oxalic acid ester conversion rate about 95%, ethylene glycol selection
Property about 90%.Hereafter a large amount of patent reports add the auxiliary agents such as Mo, Ni, Ba, Fe, Ag, La respectively in catalytic component again
The catalyst of composition, in the technique applied to oxalate synthesizing glycol.
The current status of the prior art is to be still required that a kind of activity and selectivity is higher, the better oxalate of stability
Hydrogenation catalyst.Meanwhile the catalyst should also meet the requirement that preparation process is simple, raw material is cheap and easy to get.
Summary of the invention
The present inventor passes through diligent the study found that by using SiO on the basis of existing technology2-TiO2Compound is made
It is to help using alkaline-earth metal and selected from least one of group being made of V, Cr, Zn, Fe, Ni, Co and Mn for catalyst carrier
The copper catalyst of agent, so that it may solve the problems, such as that at least one is aforementioned, and have thus completed the present invention.
Specifically, the present invention relates to the contents of following aspect.
The present invention relates to a kind of carbon monoxide-olefin polymerics.The carbon monoxide-olefin polymeric has chemical formula M-Cu-X/SiO2-
TiO2；Wherein, M is selected from least one of the group being made of the oxide of Mg, Ca, Sr and Ba；
X is selected from least one of the group being made of the oxide of V, Cr, Zn, Fe, Ni, Co and Mn；
Based on parts by weight, the content of M is 2-12 parts, and the content of Cu element is 10-40 parts, and the content of X is 2-20 parts,
SiO2-TiO2Content be 28-86 parts；SiO2-TiO2In, TiO2Account for SiO2-TiO2Weight ratio be 1-20%.
According to an aspect of the present invention, based on parts by weight, the content of M is 2-10 parts, and the content of Cu element is 15-35
Part, the content of X is 5-15 parts, SiO2-TiO2Content be 40-78 parts；SiO2-TiO2In, TiO2Account for SiO2-TiO2Weight ratio
For 5-20%.
According to an aspect of the present invention, based on parts by weight, the content of M is 3-8 parts, and the content of Cu element is 20-33
Part, the content of X is 7-13 parts, SiO2-TiO2Content be 46-70 parts；SiO2-TiO2In, TiO2Account for SiO2-TiO2Weight ratio
For 5-15%.
According to an aspect of the present invention, SiO2-TiO2In, TiO2Crystal phase structure be by anatase, rutile and plate titanium
At least one of the group of mine composition.
According to an aspect of the present invention, M is selected from least one of the group being made of the oxide of Mg, Ca and Ba.
According to an aspect of the present invention, M is selected from least one of the group being made of the oxide of Mg and Ba.
According to an aspect of the present invention, X in the group being made of the oxide of Zn, Fe, Ni, Co and Mn at least one
Kind.
According to an aspect of the present invention, X is selected from least one of the group being made of the oxide of Zn, Co and Mn.
According to an aspect of the present invention, X is selected from least one of the group being made of the oxide of Zn and Mn.
According to an aspect of the present invention, rare earth oxide is not contained in the carbon monoxide-olefin polymeric.
According to an aspect of the present invention, the rare earth element in the group being made of La, Eu, Gd and Tb at least one
Kind.
The invention further relates to the manufacturing methods of the carbon monoxide-olefin polymeric described in one kind.It the described method comprises the following steps:
A) make include silicon source solution, titanate esters and titanium oxide mixture hydrolysis, obtain carrier S iO2-TiO2；Wherein, silicon
The pH of source solution is 6-7, and the pH of mixture is 8-9；
B) make mantoquita, X salt, carrier S iO2-TiO2It is co-precipitated with precipitating reagent, obtains CuO-X/SiO2-TiO2；
C) M is made to be carried on CuO-X/SiO2-TiO2On, obtain M-CuO-X/SiO2-TiO2；
D) make M-CuO-X/SiO2-TiO2It is contacted with reducibility gas, obtains the carbon monoxide-olefin polymeric M-Cu-X/SiO2-
TiO2。
The invention further relates to the purposes that the carbon monoxide-olefin polymeric described in one kind is used to be catalyzed oxalate hydrogenation.
According to an aspect of the present invention, hydrogenation conditions include: 160-260 DEG C of reaction temperature, and oxalate weight is empty
It is 0.1-1.0 hours fast- 1, hydrogen/oxalate molar ratio (60-150): 1, reaction pressure 2.0-5.0MPa.
According to an aspect of the present invention, hydrogenation conditions include: 180-240 DEG C of reaction temperature, and oxalate weight is empty
It is 0.3-0.7 hours fast- 1, hydrogen/oxalate molar ratio is (80-120): 1, reaction pressure 2.5-3.5MPa.
Beneficial effects of the present invention: catalyst of the present invention in the reaction of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol have compared with
High activity, selectivity and stability.For example, using the method for the present invention, oxalic acid ester conversion rate reaches as high as 99.9%, phase
For the glycol selectivity answered up to 97.3%, catalyst stability is good, by operating in 6000 hours, catalyst performance not under
Drop trend.
Specific embodiment
Detailed description of the preferred embodiments below, it should be noted however that protection of the invention
Range is not limited to these specific embodiments, and but is determined by the appended claims.
All publications, patent application, patent and the other bibliography that this specification is mentioned all are incorporated by reference into
Herein.Unless otherwise defined, all technical and scientific terms used herein all there are those skilled in the art routinely to manage
The meaning of solution.In case of conflict, it is subject to the definition of this specification.
When this specification with prefix " well known to those skilled in the art ", " prior art " or its export material similar to term
Whens material, substance, method, step, device or component etc., object derived from the prefix is covered this field when the application proposes and is routinely made
Those of with, but also include also being of little use at present, it will but become art-recognized for suitable for those of similar purpose.
In the context of the present specification, other than the content clearly stated, any matters or item that do not mention are equal
It is directly applicable in those of known in the art without carrying out any change.Moreover, any embodiment described herein can be with
It is freely combined with one or more other embodiments described herein, the technical solution or technical idea formed therefrom regards
For the original disclosure of the present invention or a part of original description, and be not considered as not disclosing or be expected herein it is new in
Hold, unless those skilled in the art think that the combination is obvious unreasonable.
In the case where not clearly indicating, all percentages, number, the ratio etc. being previously mentioned in this specification be all with
On the basis of weight, unless not meeting the conventional understanding of those skilled in the art when using weight as benchmark.
In the case where not clearly indicating, the pressure being previously mentioned in this specification is all gauge pressure.
The present invention relates to a kind of carbon monoxide-olefin polymerics.The carbon monoxide-olefin polymeric has chemical formula M-Cu-X/SiO2-TiO2。
Wherein, Cu is active component, and M and X are auxiliary agent, SiO2-TiO2It is carrier.
According to the present invention, M is selected from least one of the group being made of the oxide of Mg, Ca, Sr and Ba；It is preferred that by Mg,
At least one of the group of the oxide composition of Ca and Ba；At least one in group being more preferably made of the oxide of Mg and Ba
Kind.
According to the present invention, X in the group being made of the oxide of Ti, V, Cr, Zn, Fe, Ni, Co and Mn at least one
Kind；It is preferred that at least one of the group being made of the oxide of Zn, Fe, Ni, Co and Mn；More preferably by the oxidation of Zn, Co and Mn
At least one of the group of object composition；At least one of the group being most preferably made of the oxide of Zn and Mn.
According to the present invention, based on parts by weight, the content of M is 2-12 parts, and the content of Cu element is 10-40 parts, the content of X
It is 2-20 parts, SiO2-TiO2Content be 28-86 parts；Preferably, the content of M is 2-10 parts, and the content of Cu element is 15-35
Part, the content of X is 5-15 parts, SiO2-TiO2Content be 40-78 parts；More preferably, the content of M is 3-8 parts, and Cu element contains
Amount is 20-33 parts, and the content of X is 7-13 parts, SiO2-TiO2Content be 46-70 parts.
According to the present invention, carrier SiO2-TiO2Compound, rather than SiO2And TiO2Mechanical impurity.Carrier S iO2-
TiO2In, TiO2Account for SiO2-TiO2Weight ratio be 1-20%, preferably 5-20%, more preferably 5-15%.
According to the present invention, SiO2-TiO2In, TiO2Crystal phase structure be by anatase (AT), rutile (RT) and brockite
(BT) at least one of the group formed.
According to the present invention, rare earth oxide is not contained in carbon monoxide-olefin polymeric.Especially without containing La, Eu, Gd and
The oxide of Tb.
The invention further relates to a kind of manufacturing methods of carbon monoxide-olefin polymeric.The manufacturing method the following steps are included:
A) make include silicon source solution, titanate esters and titanium oxide mixture hydrolysis, obtain carrier S iO2-TiO2；Wherein, silicon
The pH of source solution is 6-7, and the pH of mixture is 8-9；
B) make mantoquita, X salt, carrier S iO2-TiO2It is co-precipitated with precipitating reagent, obtains CuO-X/SiO2-TiO2；
C) M is made to be carried on CuO-X/SiO2-TiO2On, obtain M-CuO-X/SiO2-TiO2；
D) make M-CuO-X/SiO2-TiO2It is contacted with reducibility gas, obtains the carbon monoxide-olefin polymeric M-Cu-X/SiO2-
TiO2。
According to the present invention, in step a), silicon source solution can be sodium silicate aqueous solution.Titanate esters can be metatitanic acid tetrem
Ester, four n-propyl of metatitanic acid, tetraisopropyl titanate, tetra-n-butyl titanate and tetrabutyl titanate or its mixture.Titanium oxide can
To be anatase (AT), rutile (RT), brockite (BT) or its mixture.The pH value control of silicon source solution is 6-7, control
The method of system is well known to those skilled in the art, such as is adjusted with acid, and acid can be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid,
Either its aqueous solution.Mixture including silicon source solution, titanate esters and titanium oxide, pH value control are 8-9, the method for control
It is equally well known to those skilled in the art, such as is adjusted with alkali, alkali can be ammonium hydroxide, sodium hydroxide, potassium hydroxide, hydrogen
Rubidium oxide or its aqueous solution.The hydrolysis time of mixture is 4-24 hours.
It according to the present invention,, can be by any point known to the art after hydrolysing step terminates in step a)
The carrier S iO of preparation is isolated from product mixtures obtained from method2-TiO2.As the separate mode, such as can
To enumerate the method that the product mixtures of the acquisition are filtered, wash, dry and are roasted.Here, described filter, wash
Washing, dry and roasting can carry out according to conventionally known in the art any mode.For concrete example, as the filtering,
Such as it can simply filter the product mixtures of the acquisition.As the washing, for example, using deionized water
It is washed.As the drying temperature, for example, 80-160 DEG C, as the drying time, for example,
4-24 hours.The drying can carry out under normal pressure, can also carry out under reduced pressure.As the maturing temperature, such as can be with
350-650 DEG C is enumerated, as the calcining time, for example, 2-8 hours.In addition, the roasting is generally oxygenous
It is carried out under atmosphere, such as under air or oxygen atmosphere.
According to the present invention, step b) is to prepare CuO-X/SiO using coprecipitation2-TiO2.Coprecipitation is also this field
It is known, i.e. mantoquita, X salt, carrier S iO2-TiO2It is co-precipitated with precipitating reagent.Specifically, mantoquita and X salt are added to the water, are obtained
To mixed solution A；Precipitating reagent is added to the water, solution B is obtained；The carrier S iO that step a) is obtained2-TiO2It is scattered in water, it will
Suspension is heated to 40-80 DEG C, and it is that 6-7 carries out aging, gained that solution A and solution B, which are added in the suspension, and keep pH value
Precipitating is CuO-X/SiO2-TiO2.Wherein, mantoquita and X salt can be nitrate, acylate or its mixture.Precipitating
Agent can be ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate or its mixture.Always
Changing temperature is 40-90 DEG C, and the time is 2-24 hours.
It according to the present invention,, can be by any known to the art after co-precipitation step terminates in step b)
Separation method isolates the intermediary CuO-X/SiO of preparation from product mixtures obtained2-TiO2.As the separation side
Formula, for example the method that the product mixtures of the acquisition are filtered, wash, dry and are roasted can be enumerated.Here, described
Being filtered, washed, dry and roasting can carry out according to conventionally known in the art any mode.For concrete example, as institute
Filtering is stated, such as can simply filter the product mixtures of the acquisition.As the washing, for example, using going
Ionized water is washed.As the drying temperature, for example, 80-160 DEG C, as the drying time, such as can
To enumerate 4-24 hours.The drying can carry out under normal pressure, can also carry out under reduced pressure.As the maturing temperature, example
350-650 DEG C can be such as enumerated, as the calcining time, for example, 2-8 hours.In addition, the roasting generally exists
It is carried out under oxygen-containing atmosphere, such as under air or oxygen atmosphere.
According to the present invention, step c) is that alkaline-earth metal M is carried on intermediary CuO-X/SiO2-TiO2On.Load the side of M
Method can use infusion process known in the art.Specifically, by intermediary CuO-X/SiO2-TiO2It is scattered in M salting liquid,
Up to presoma M-CuO-X/SiO2-TiO2。
It according to the present invention,, can be by any point known to the art after impregnation steps terminate in step c)
The presoma M-CuO-X/SiO of preparation is isolated from product mixtures obtained from method2-TiO2.As the separation side
Formula, for example the method that the product mixtures of the acquisition are filtered, wash, dry and are roasted can be enumerated.Here, described
Being filtered, washed, dry and roasting can carry out according to conventionally known in the art any mode.For concrete example, as institute
Filtering is stated, such as can simply filter the product mixtures of the acquisition.As the washing, for example, using going
Ionized water is washed.As the drying temperature, for example, 80-160 DEG C, as the drying time, such as can
To enumerate 4-24 hours.The drying can carry out under normal pressure, can also carry out under reduced pressure.As the maturing temperature, example
350-650 DEG C can be such as enumerated, as the calcining time, for example, 2-8 hours.In addition, the roasting generally exists
It is carried out under oxygen-containing atmosphere, such as under air or oxygen atmosphere.
According to the present invention, step d) makes presoma M-CuO-X/SiO2-TiO2It is contacted with reducibility gas, obtains described urge
Agent composition M-Cu-X/SiO2-TiO2.Reducibility gas is H2The gaseous mixture of inert gas, inert gas can be N2Or
At least one of person Ar, hydrogen volume content is 5-30% in gaseous mixture, and the flow of gaseous mixture is 10-150 ml/min gram
Catalyst；Reduction temperature is preferably 200-400 DEG C, and the recovery time is preferably 8-20 hours.
The invention further relates to the purposes that the carbon monoxide-olefin polymeric described in one kind is used to be catalyzed oxalate hydrogenation.Raw material grass
Acid esters and hydrogen contact under hydrogenation conditions with catalyst, obtain the effluent containing ethylene glycol.
According to the present invention, hydrogenation conditions include: 160-260 DEG C of reaction temperature, and oxalate weight space velocity 0.1-1.0 is small
When- 1, hydrogen/oxalate molar ratio (60-150): 1, reaction pressure 2.0-5.0MPa；It is preferred that 180-240 DEG C of reaction temperature, oxalic acid
Ester weight space velocity 0.3-0.7 hours- 1, hydrogen/oxalate molar ratio is (80-120): 1, reaction pressure 2.5-3.5MPa.
The present invention will be further described below by way of examples.
[embodiment 1]
234.5 gram of nine water sodium metasilicate is dissolved in 800 milliliters of water, and the dilute sulfuric acid for being added with stirring 5wt% adjusts pH to 6-7,
Then 23.4 grams of tetra-n-butyl titanates and 5 grams of AT-TiO are added2Powder, after mixing evenly, with 5wt% sodium hydroxide solution tune
PH to 8-9 is saved, after hydrolyzing 12h, filtering after being washed with deionized, obtains after 500 DEG C of roasting 4h after 120 DEG C of dry 16h
SiO2-TiO2Catalyst carrier ST-1.
113.4 grams of nitrate trihydrate copper and 36.7 grams of zinc nitrate hexahydrates are dissolved in 500 milliliters of water, solution A 1 is obtained；It will
65.9 grams of natrium carbonicum calcinatums are dissolved in 500 milliliters of water, obtain solution B 1；It disperses 54.0g carrier S T-1 in 300 milliliters of water,
60 DEG C are heated to, with vigorous stirring, solution A 1 and B1 is added dropwise in above-mentioned dispersion liquid simultaneously, temperature is kept during dropwise addition
Degree is 60 DEG C and pH value is 6-7, and after terminating after 60 DEG C of aging 10h, precipitating is washed with deionized in filtering, dry at 120 DEG C
Intermediary PST-1 is obtained in 450 DEG C of roasting 4h after dry 16h.
It disperses 94 grams of intermediary PST-1 in 500 milliliters of water, 10.2 grams of barium nitrates is then added wherein, are warming up to
Catalyst precursor MPST-1 is obtained in 450 DEG C of roasting 4h after 120 DEG C of dry 16h after 80 DEG C of solvent evaporateds.
The H for being 25% with hydrogen volume content2-N2Gaseous mixture restores 10 hours the solids at 320 DEG C, gaseous mixture
Flow is 140 ml/min gram catalyst, and M-Cu-X/SiO is just made2-TiO2Catalyst C1.
In catalyst C1, the parts by weight that the parts by weight that the parts by weight of M (Ba) are 6.1, Cu are 29.9, X (Zn) are
10.0, carrier S iO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 9.8%.
[embodiment 2]
The preparation method of catalyst carrier ST-2 is identical as in [embodiment 1], only nine water sodium metasilicate and titanium used
The amount of sour four N-butyls is respectively 255.1 grams and 4.7 grams, and BT-TiO is added22.5 grams of powder, AT-TiO2It is 2.5 grams of powder, intermediate
Object PST-2, presoma MPST-2 and restoring method are identical as [embodiment 1], obtain catalyst C2.
In catalyst C2, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
SiO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 1.8%.
[embodiment 3]
The preparation method of catalyst carrier ST-3 is identical as in [embodiment 1], only nine water sodium metasilicate and titanium used
The amount of sour four N-butyls is respectively 247.3 grams and 11.7 grams, and RT-TiO is added25 grams of powder, intermediary PST-3, presoma
MPST-3 and restoring method are identical as [embodiment 1], obtain catalyst C3.
In catalyst C3, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
SiO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 5.1%.
[embodiment 4]
The preparation method of catalyst carrier ST-4 is identical as in [embodiment 1], only nine water sodium metasilicate and titanium used
The amount of sour four N-butyls is respectively 221.3 grams and 35.1 grams, and BT-TiO is added25 grams of powder, intermediary PST-4, presoma
MPST-4 and restoring method are identical as [embodiment 1], obtain catalyst C4.
In catalyst C4, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
SiO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 15.1%.
[embodiment 5]
The preparation method of catalyst carrier ST-5 is identical as in [embodiment 1], only nine water sodium metasilicate and titanium used
The amount of sour four N-butyls is respectively 210.9 grams and 44.4 grams, intermediary PST-5, presoma MPST-5 and restoring method and [implementation
Example 1] it is identical, obtain catalyst C5.
In catalyst C5, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
SiO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 19.1%.
[comparative example 1]
The preparation method of catalyst carrier CST-1 is identical as in [embodiment 1], only the amount of nine water sodium metasilicate used
It is 255.6 grams, is added without tetra-n-butyl titanate and titanium dioxide powder.Intermediary CPST-1, presoma CMPST-1 and restoring method
It is identical as [embodiment 1], obtain catalyst CC1.
In catalyst CC1, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
For SiO2, be free of TiO2, parts by weight 54.
[embodiment 6]
234.5 gram of nine water sodium metasilicate is dissolved in 800 milliliters of water, and the dilute hydrochloric acid that 5wt% is added under stiring adjusts pH to 6-
7,19.5 grams of tetraisopropyl titanates and 5 grams of AT-TiO are then added2Powder, after mixing evenly, with 5wt% ammonium hydroxide adjust pH to
8-9, after hydrolysis for 24 hours, filtering after being washed with deionized, obtains SiO after 600 DEG C of roasting 7h after 150 DEG C of dry 20h2-
TiO2Catalyst carrier ST-6.
93.8 gram of one water acetic acid copper and 27.0 grams of zinc acetate dihydrates are dissolved in 500 milliliters of water, solution A 6 is obtained；By 75.5
The concentrated ammonia liquor of gram 28wt% is added in 500 milliliters of water, obtains solution B 6；It disperses 55.0g carrier S T-6 in 300 milliliters of water,
80 DEG C are heated to, with vigorous stirring, solution A 6 and B6 is added dropwise in above-mentioned dispersion liquid simultaneously, temperature is kept during dropwise addition
Degree is 80 DEG C and pH value is 6-7, and after terminating after 90 DEG C of aging 23h, precipitating is washed with deionized in filtering, dry at 90 DEG C
It is dry for 24 hours after in 600 DEG C of roasting 8h obtain intermediary PST-6.
It disperses 94 grams of intermediary PST-1 in 500 milliliters of water, 10.4 grams of barium acetates is then added wherein, are warming up to
Catalyst precursor MPST-6 is obtained in 600 DEG C of roasting 4h after 150 DEG C of dry 22h after 95 DEG C of solvent evaporateds.
The H for being 10% with hydrogen volume content2- Ar gaseous mixture restores 18 hours the solids at 250 DEG C, gaseous mixture
Flow is 30 ml/min gram catalyst, and M-Cu-X/SiO is just made2- TiO2 catalyst C6.
In catalyst C6, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, carrier
SiO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 9.8%.
[embodiment 7]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 61.1 grams, and the amount of zinc nitrate hexahydrate is 11.0 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 56.3 grams, obtains intermediary PST-7.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C7.
In catalyst C7, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 3.1, carrier
SiO2-TiO2Parts by weight be 60.9, TiO in carrier2Weight content be 9.8%.
[embodiment 8]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 57.0 grams, and the amount of zinc nitrate hexahydrate is 25.7 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 61.8 grams, obtains intermediary PST-8.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C8.
In catalyst C8, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 7.0, carrier
SiO2-TiO2Parts by weight be 57.0, TiO in carrier2Weight content be 9.8%.
[embodiment 9]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 51.0 grams, and the amount of zinc nitrate hexahydrate is 47.7 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 70.0 grams, obtains intermediary PST-9.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C9.
In catalyst C9, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 13.0, carrier
SiO2-TiO2Parts by weight be 51.0, TiO in carrier2Weight content be 9.8%.
[embodiment 10]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 45.0 grams, and the amount of zinc nitrate hexahydrate is 69.7 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 78.3 grams, obtains intermediary PST-10.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C10.
In catalyst C10, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 19.0, are carried
Body SiO2-TiO2Parts by weight be 45.0, TiO in carrier2Weight content be 9.8%.
[comparative example 2]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary CPST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 64.0 grams, is added without zinc nitrate hexahydrate, precipitating reagent is anhydrous
The amount of sodium carbonate is 52.2 grams, obtains intermediary CPST-2.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst CC2.
In catalyst CC2, the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, are free of X, carrier S iO2-TiO2's
Parts by weight are 64.0, TiO in carrier2Weight content be 9.8%.
[embodiment 11]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 73.0 grams, and the amount of Gerhardite is 41.6 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 32.9 grams, obtains intermediary PST-11.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C11.
In catalyst C11, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 10.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 73.0, TiO in carrier2Weight content be 9.8%.
[embodiment 12]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 65.0 grams, and the amount of Gerhardite is 71.8 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 46.8 grams, obtains intermediary PST-12.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C12.
In catalyst C12, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 18.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 65.0, TiO in carrier2Weight content be 9.8%.
[embodiment 13]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 59.0 grams, and the amount of Gerhardite is 94.5 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 57.2 grams, obtains intermediary PST-13.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C13.
In catalyst C13, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 24.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 59.0, TiO in carrier2Weight content be 9.8%.
[embodiment 14]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 45.0 grams, and the amount of Gerhardite is 147.5 grams, precipitating
The amount of agent natrium carbonicum calcinatum is 81.6 grams, obtains intermediary PST-14.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C14.
In catalyst C14, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 38.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 45.0, TiO in carrier2Weight content be 9.8%.
[embodiment 15]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 58.0 grams, obtains intermediary PST-15.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], only Ba (NO used3)2Amount be
4.3 grams, the amount of PST-15 is 97.9 grams, obtains catalyst C15.
In catalyst C15, the parts by weight that the parts by weight that the parts by weight of M are 2.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 58.0, TiO in carrier2Weight content be 9.8%.
[embodiment 16]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 56.0 grams, obtains intermediary PST-16.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], only Ba (NO used3)2Amount be
6.8 grams, the amount of PST-16 is 95.9 grams, obtains catalyst C16.
In catalyst C16, the parts by weight that the parts by weight that the parts by weight of M are 4.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 56.0, TiO in carrier2Weight content be 9.8%.
[embodiment 17]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 53.0 grams, obtains intermediary PST-17.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], only Ba (NO used3)2Amount be
11.9 grams, the amount of PST-17 is 92.9 grams, obtains catalyst C17.
In catalyst C17, the parts by weight that the parts by weight that the parts by weight of M are 7.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 53.0, TiO in carrier2Weight content be 9.8%.
[embodiment 18]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 49.0 grams, obtains intermediary PST-18.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], only Ba (NO used3)2Amount be
18.8 grams, the amount of PST-18 is 88.9 grams, obtains catalyst C18.
In catalyst C18, the parts by weight that the parts by weight that the parts by weight of M are 11.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 49.0, TiO in carrier2Weight content be 9.8%.
[comparative example 3]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary CPST
Process is identical as [embodiment 1], and only the amount of ST-1 used is 60.0 grams, obtains intermediary CPST-3.
The present embodiment is modified without alkaline-earth metal, and the restoring method of catalyst is identical as [embodiment 1], obtains catalyst
CC3。
In catalyst CC3, the parts by weight that the parts by weight that the parts by weight of M are 0, Cu are 30.0, X are 10.0, carrier
SiO2-TiO2Parts by weight be 60.0, TiO in carrier2Weight content be 9.8%.
[embodiment 19]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only 36.7 grams of zinc nitrate hexahydrates used are replaced with 41.4 grams of 50wt% manganese nitrate aqueous solutions,
The amount of precipitating reagent natrium carbonicum calcinatum is 65.0 grams, obtains intermediary PST-19.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C19.
In catalyst C19, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 54.0, TiO in carrier2Weight content be 9.8%.
[embodiment 20]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only 36.7 grams of zinc nitrate hexahydrates used are replaced with 50.5 gram of nine water ferric nitrate, precipitating reagent without
The amount of aqueous sodium carbonate is 73.1 grams, obtains intermediary PST-20.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C20.
In catalyst C20, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 54.0, TiO in carrier2Weight content be 9.8%.
[embodiment 21]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only 36.7 grams of zinc nitrate hexahydrates used are replaced with 35.1 grams of cobalt nitrate hexahydrates, precipitating reagent without
The amount of aqueous sodium carbonate is 65.6 grams, obtains intermediary PST-21.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C21.
In catalyst C21, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 54.0, TiO in carrier2Weight content be 9.8%.
[embodiment 22]
Catalyst carrier SiO2-TiO2Preparation method it is identical as [embodiment 1], obtain ST-1, the preparation of intermediary PST
Process is identical as [embodiment 1], and only 36.7 grams of zinc nitrate hexahydrates used are replaced with 35.1 gram of six water nickel nitrate, precipitating reagent without
The amount of aqueous sodium carbonate is 65.6 grams, obtains intermediary PST-22.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], obtains catalyst C22.
In catalyst C22, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 54.0, TiO in carrier2Weight content be 9.8%.
[embodiment 23]
Catalyst carrier SiO2-TiO2, intermediary PST preparation method it is identical as [embodiment 1], obtain ST-1 and PST-1.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], and only alkali salt used is
38.4 grams of magnesium nitrate hexahydrates, obtain catalyst C23.
In catalyst C23, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 54.0, TiO in carrier2Weight content be 9.8%.
[embodiment 24]
Catalyst carrier SiO2-TiO2, intermediary PST preparation method it is identical as [embodiment 1], obtain ST-1 and PST-1.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], and only alkali salt used is
25.3 grams of four water-calcium nitrates, obtain catalyst C24.
In catalyst C24, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 54.0, TiO in carrier2Weight content be 9.8%.
[embodiment 25]
Catalyst carrier SiO2-TiO2, intermediary PST preparation method it is identical as [embodiment 1], obtain ST-1 and PST-1.
The restoring method of alkaline-earth metal modification and catalyst is identical as [embodiment 1], and only alkali salt used is
12.1 grams of strontium nitrates, obtain catalyst C25.
In catalyst C25, the parts by weight that the parts by weight that the parts by weight of M are 6.1, Cu are 29.9, X are 10.0, are carried
Body SiO2-TiO2Parts by weight be 55.0, TiO in carrier2Weight content be 9.8%.
[comparative example 4]
The preparation method of catalyst carrier CST-4 is identical as in [embodiment 1], and nine water sodium metasilicate are only not added.It is intermediate
Object CPST-4, presoma CMPST-4 and restoring method are identical as [embodiment 1], obtain catalyst CC4.
In catalyst CC4, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
For AT-TiO2, be free of SiO2, parts by weight 54.
[comparative example 5]
The preparation method of catalyst carrier CST-5 is identical as in [embodiment 1], and nine water sodium metasilicate are only not added, and
By AT-TiO2Powder replaces with RT- titanium dioxide powder.Intermediary CPST-5, presoma CMPST-5 and restoring method and [implementation
Example 1] it is identical, obtain catalyst CC5.
In catalyst CC5, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
For RT-TiO2, be free of SiO2, parts by weight 54.
[comparative example 6]
The preparation method of catalyst carrier CST-6 is identical as in [embodiment 1], and nine water sodium metasilicate are only not added, and
By AT-TiO2Powder replaces with BT- titanium dioxide powder.Intermediary CPST-6, presoma CMPST-6 and restoring method and [implementation
Example 1] it is identical, obtain catalyst CC6.
In catalyst CC6, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
For BT-TiO2, be free of SiO2, parts by weight 54.
[comparative example 7]
The preparation method of catalyst carrier CST-7 is identical as in [embodiment 1], and only zinc nitrate used is by lanthanum nitrate
Replace.Intermediary CPST-7, presoma CMPST-7 and restoring method are identical as [embodiment 1], obtain catalyst CC7.
In catalyst CC7, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of La are 10.0, are free of
Zn, carrier S iO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 9.8%.
[comparative example 8]
The preparation method of catalyst carrier CST-8 is identical as in [embodiment 1], and only zinc nitrate used is by europium nitrate
Replace.Intermediary CPST-8, presoma CMPST-8 and restoring method are identical as [embodiment 1], obtain catalyst CC8.
In catalyst CC8, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of Eu are 10.0, are free of
Zn, carrier S iO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 9.8%.
[comparative example 9]
The preparation method of catalyst carrier CST-9 is identical as in [embodiment 1], and only silicon source pH value of solution is adjusted to 8；System
PH to 9 is adjusted with 5wt% sodium hydroxide solution during standby.Intermediary CPST-9, presoma CMPST-9 and restoring method with
[embodiment 1] is identical, obtains catalyst CC9.
In catalyst CC9, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
SiO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 9.8%.
[comparative example 10]
The preparation method of catalyst carrier CST-10 is identical as in [embodiment 1], and only silicon source pH value of solution is adjusted to 5；
PH to 6 is adjusted with 5wt% sodium hydroxide solution in preparation process.Intermediary CPST-10, presoma CMPST-10 and restoring method
It is identical as [embodiment 1], obtain catalyst CC10.
In catalyst CC10, the parts by weight of M are the parts by weight 29.9 of 6.1, Cu, and the parts by weight of X are 10.0, carrier
SiO2-TiO2Parts by weight be 54, TiO in carrier2Weight content be 9.8%.
The catalyst C1-25 of [embodiment 1-25], and the composition of catalyst CC1-3 of [comparative example 1-3] are shown in Table 1.
[embodiment 26-50]
This example demonstrates that application of the catalyst obtained by [embodiment 1-25] in hydrogenation of oxalate for preparing ethylene glycol (EG).
Take the stainless steel that each 10 grams of loadings internal diameter of catalyst C1-C26 obtained by [embodiment 1-25] of the invention is 20 millimeters anti-
Ying Guanzhong, is passed through dimethyl oxalate (DMO) and hydrogen carries out reaction examination.Catalyst is in the case where pressure is 3.0MPa, temperature 210
DEG C, air speed 0.5h-1, hydrogen ester molar ratio be 100 under conditions of reacted, hydrogenation products include methyl glycollate (MG), second
Alcohol (ET) and 1,2- butanediol (BDO) etc..Reaction result is listed in table 2.Table 1
| Catalyst | Cu number | M number | X number | Titanium oxide ratio in carrier |
| C1 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| C2 | 29.9 | Ba 6.1 | Zn 10 | 1.8 |
| C3 | 29.9 | Ba 6.1 | Zn 10 | 5.1 |
| C4 | 29.9 | Ba 6.1 | Zn 10 | 15.1 |
| C5 | 29.9 | Ba 6.1 | Zn 10 | 19.1 |
| CC1 | 29.9 | Ba 6.1 | Zn 10 | 0 |
| C6 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| C7 | 29.9 | Ba 6.1 | Zn 3.1 | 9.8 |
| C8 | 29.9 | Ba 6.1 | Zn 7 | 9.8 |
| C9 | 29.9 | Ba 6.1 | Zn 13 | 9.8 |
| C10 | 29.9 | Ba 6.1 | Zn 19 | 9.8 |
| CC2 | 29.9 | Ba 6.1 | 0 | 9.8 |
| C11 | 10.9 | Ba 6.1 | Zn 10 | 9.8 |
| C12 | 18.9 | Ba 6.1 | Zn 10 | 9.8 |
| C13 | 24.9 | Ba 6.1 | Zn 10 | 9.8 |
| C14 | 38.9 | Ba 6.1 | Zn 10 | 9.8 |
| C15 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| C16 | 29.9 | Ba 4.1 | Zn 10 | 9.8 |
| C17 | 29.9 | Ba 7.1 | Zn 10 | 9.8 |
| C18 | 29.9 | Ba 11.1 | Zn 10 | 9.8 |
| CC3 | 30 | 0 | Zn 10 | 9.8 |
| C19 | 29.9 | Ba 6.1 | Mn 10 | 9.8 |
| C20 | 29.9 | Ba 6.1 | Fe 10 | 9.8 |
| C21 | 29.9 | Ba 6.1 | Co 10 | 9.8 |
| C22 | 29.9 | Ba 6.1 | Ni 10 | 9.8 |
| C23 | 29.9 | Mg 6.1 | Zn 10 | 9.8 |
| C24 | 29.9 | Ca 6.1 | Zn 10 | 9.8 |
| C25 | 29.9 | Sr 6.1 | Zn 10 | 9.8 |
| CC4 | 29.9 | Ba 6.1 | Zn 10 | 100 |
| CC5 | 29.9 | Ba 6.1 | Zn 10 | 100 |
| CC6 | 29.9 | Ba 6.1 | Zn 10 | 100 |
| CC7 | 29.9 | Ba 6.1 | La 10 | 9.8 |
| CC8 | 29.9 | Ba 6.1 | Eu 10 | 9.8 |
| CC9 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
| CC10 | 29.9 | Ba 6.1 | Zn 10 | 9.8 |
Table 2
[comparative example 11-20]
The examination condition of catalyst is identical as [embodiment 26], obtains that the results are shown in Table 3.
Table 3
[embodiment 51-55]
Change condition used in catalyst test, other conditions are identical as [embodiment 26], obtained result such as 4 institute of table
Show.
Table 4
[embodiment 56]
The service life of catalyst C1 is checked and rated, condition is identical as [embodiment 26], obtains that the results are shown in Table 5.
Table 5
| Reaction time (h) | XDMO(%) | SEG(%) |
| 1000 | 100 | 96.3 |
| 2000 | 100 | 96.2 |
| 3000 | 100 | 96.1 |
| 4000 | 100 | 96 |
| 5000 | 99.9 | 96.2 |
| 6000 | 99.8 | 96.1 |
[comparative example 21]
The service life of catalyst CC1 is checked and rated, condition is identical as [embodiment 26], obtains that the results are shown in Table 6.
Table 6
| Reaction time (h) | XDMO(%) | SEG(%) |
| 100 | 90.1 | 84.4 |
| 200 | 88.5 | 83.5 |
| 300 | 86.3 | 82.4 |
Claims (15)
1. a kind of carbon monoxide-olefin polymeric has chemical formula M-Cu-X/SiO2-TiO2；Wherein, M is selected from the oxygen by Mg, Ca, Sr and Ba
At least one of the group of compound composition；
X is selected from least one of the group being made of the oxide of V, Cr, Zn, Fe, Ni, Co and Mn；
Based on parts by weight, the content of M is 2-12 parts, and the content of Cu element is 10-40 parts, and the content of X is 2-20 parts, SiO2-
TiO2Content be 28-86 parts；SiO2-TiO2In, TiO2Account for SiO2-TiO2Weight ratio be 1-20%.
2. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that based on parts by weight, the content of M is 2-10
Part, the content of Cu element is 15-35 parts, and the content of X is 5-15 parts, SiO2-TiO2Content be 40-78 parts；SiO2-TiO2In,
TiO2Account for SiO2-TiO2Weight ratio be 5-20%.
3. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that based on parts by weight, the content of M is 3-8 parts,
The content of Cu element is 20-33 parts, and the content of X is 7-13 parts, SiO2-TiO2Content be 46-70 parts；SiO2-TiO2In, TiO2
Account for SiO2-TiO2Weight ratio be 5-15%.
4. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that SiO2-TiO2In, TiO2Crystal phase structure be
At least one of the group being made of anatase, rutile and brockite.
5. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that M is selected from and is made of the oxide of Mg, Ca and Ba
At least one of group.
6. carbon monoxide-olefin polymeric according to claim 5, which is characterized in that M is selected to be made of the oxide of Mg and Ba
At least one of group.
7. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that X is selected from the oxidation by Zn, Fe, Ni, Co and Mn
At least one of the group of object composition.
8. carbon monoxide-olefin polymeric according to claim 7, which is characterized in that X is selected from and is made of the oxide of Zn, Co and Mn
At least one of group.
9. carbon monoxide-olefin polymeric according to claim 8, which is characterized in that X is selected to be made of the oxide of Zn and Mn
At least one of group.
10. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that without containing dilute in the carbon monoxide-olefin polymeric
Earth elements oxide.
11. carbon monoxide-olefin polymeric according to claim 10, which is characterized in that the rare earth element is selected from by La, Eu, Gd
With at least one of the group of Tb composition.
12. the preparation method of any carbon monoxide-olefin polymeric of claim 1-11, comprising the following steps:
A) make include silicon source solution, titanate esters and titanium oxide mixture hydrolysis, obtain carrier S iO2-TiO2；Wherein, silicon source is molten
The pH of liquid is 6-7, and the pH of mixture is 8-9；
B) make mantoquita, X salt, carrier S iO2-TiO2It is co-precipitated with precipitating reagent, obtains CuO-X/SiO2-TiO2；
C) M is made to be carried on CuO-X/SiO2-TiO2On, obtain M-CuO-X/SiO2-TiO2；
D) make M-CuO-X/SiO2-TiO2It is contacted with reducibility gas, obtains the carbon monoxide-olefin polymeric M-Cu-X/SiO2-TiO2。
13. the purposes that any carbon monoxide-olefin polymeric of claim 1-11 is used to be catalyzed oxalate hydrogenation.
14. the 3 agent compositions are used to be catalyzed the purposes of oxalate hydrogenation according to claim 1, which is characterized in that add
Hydroformylation reaction condition includes: 160-260 DEG C of reaction temperature, and oxalate weight space velocity 0.1-1.0 hours- 1, hydrogen/oxalate molar ratio
(60-150): 1, reaction pressure 2.0-5.0MPa.
15. the 4 agent compositions are used to be catalyzed the purposes of oxalate hydrogenation according to claim 1, which is characterized in that add
Hydroformylation reaction condition includes: 180-240 DEG C of reaction temperature, and oxalate weight space velocity 0.3-0.7 hours- 1, hydrogen/oxalate molar ratio
For (80-120): 1, reaction pressure 2.5-3.5MPa.
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