CN106607024A - Catalyst for preparing oxalate through CO gas phase synthesis and preparation method and application thereof - Google Patents
Catalyst for preparing oxalate through CO gas phase synthesis and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing oxalate through CO gas phase synthesis and a preparation method and application of the catalyst. The catalyst is mainly used for solving the problems that activity and selectivity are low and stability is poor in the prior art. According to the adopted technical scheme, the catalyst comprises, by weight, an active component, an additive, a modifying agent and a carrier, wherein palladium is adopted as the active component with the using amount elementally accounting for 0.1-4.0% of the weight of the carrier, a rare earth element is adopted as the modifying agent with the using amount elementally accounting for 0.1-3.0% of the weight of the carrier, aluminum oxide is used the carrier which is modified by the rare earth element, the specific area of the aluminum oxide carrier is 3-40 m<2>/g, and the pore volume with the pore diameter being 15-40 nanometers accounts for 75%-95% of the total pore volume. Accordingly, the problems are well solved, and the catalyst can be used in industrial production for preparing oxalate through CO gas phase synthesis.
Description
Technical field
The present invention relates to a kind of catalyst, the Preparation method and use of CO gas-phase synthesis of oxalate.
Background technology
Oxalate is important industrial chemicals, can be used to prepare the intermediate of oxalic acid, ethylene glycol, carbonic ester, medicine and dyestuff,
Plastics accelerator and solvent etc..The synthetic method of traditional dimethyl oxalate is the esterification using oxalic acid and methyl alcohol, and it is led
The oxalic acid for wanting one of raw material is produced with sodium formate method, by carbon monoxide and NaOH at 160 DEG C, under 18-20kg pressure,
Synthesising acid sodium, is then dehydrogenated to sodium oxalate in 400 DEG C of concentrations, then generates lead oxalate with lead sulfate effect, further uses sulphur
Acid is acidified to obtain oxalic acid crude product, finally with brium carbonate and centesimal polyacrylamide coagulative precipitation, obtains refined oxalic acid, but,
Its technological process of production is long, and high energy consumption, pollution are big, relatively costly, needs to find new production technology.By CO and nitrous
Sour methyl esters gas-phase catalytic coupling synthesis of oxalate open one from the raw material of carbon one produce oxalic acid new route, 80 years
Since generation, foreign countries report successively the new development of oxalic acid synthesis.
Japan Patent JP8242656 Application Publications disclose first a strip adoption platinum group metal loaded catalyst carry out CO with
The technological process of methyl nitrite synthesizing dimethyl oxalate, the space-time yield of catalyst is 432g/Lh, and Jing 480 hours is continuous
Reaction, yield is not reduced.
United States Patent (USP) US4334433 discloses Pd-Mo/Al2O3And Pd-Ni/Al2O3Catalyst, at ambient pressure, 110 DEG C and
Air speed 2000h-1, initial feed gas composition：CH3ONO-15%, CO-20%, CH3OH-15%, NO-3%, N2- 47%
Under conditions of (volumetric concentration, the concentration of following all gas refers both to volumetric concentration), dimethyl oxalate space-time yield is
400g/Lh, the selectivity for generating dimethyl oxalate by CO reaches 95%.
United States Patent (USP) US4507494 discloses a kind of Pd-Ti/Al2O3Catalyst, at pressure 0.24MPa, 115-120 DEG C and
Air speed 3000h-1, initial feed gas composition：CH3ONO-10%, CO-20%, CH3OH-4%, NO-3%, N2- 63%
Under conditions of, successive reaction 950 hours, dimethyl oxalate space-time yield is 429-462g/Lh, and by CO oxalic acid two is generated
The selectivity of methyl esters reaches 95%.
Chinese patent CN95116136.9 discloses a kind of oxalate catalyst for synthesizing, and brill makees auxiliary agent, uses infusion process with Zr
It is prepared for Pd-Zr/Al2O3Catalyst.CO is carried out with nitrites synthesis grass using the catalyst on fixed-bed reactor
Acid esters reacts, but in the invention catalyst oxalate yield it is low, and higher, product oxalate is required to the impurity of unstripped gas
Selectivity 95%, the conversion per pass of nitrites is only up to 64%.
Hereafter a large amount of patent reports add Mo, Ni, Ti, Fe, Ga, Cu, Na respectively in catalytic component again2O
And SiO2Deng the catalyst of auxiliary agent composition, in being applied to the technique of CO and methyl nitrite synthesis of oxalate, but space-time yield
All than relatively low.
The content of the invention
One of the technical problem to be solved is that have that activity and selectivity is low, the technology that stability is poor in prior art
A kind of problem, there is provided new CO catalyst for synthesizing oxalic ester by gas-phase, the catalyst is in carbon monoxide and nitrites synthesis grass
There is higher activity and selectivity in acid esters reaction, and bed temperature is reasonably distributed, and can tolerate hydrogen, vapor etc. miscellaneous
The impact of matter, life-span length, react it is easily controllable the advantages of.The two of the technical problem to be solved be to provide it is a kind of with
Solve the preparation method of one of technical problem corresponding catalyst.The three of the technical problem to be solved are to provide one
The purposes planted and solve one of technical problem corresponding catalyst for the reaction of CO gas-phase synthesis of oxalate.
To solve one of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of CO gas-phase synthesis of oxalate
Catalyst, including carrier, active component, auxiliary agent and/or modifying agent, by weight percentage, catalyst includes following component：
A) with palladium as active component, 0.1-4.0% of the consumption as vehicle weight is counted with simple substance；
B) with zinc as auxiliary agent, 0.05-2.0% of the consumption as vehicle weight is counted with simple substance；
C) with rare earth element as auxiliary agent or modifying agent, 0.1-3.0% of the consumption as vehicle weight is counted with simple substance；
D) with least one of aluminum oxide or silica as carrier.
In above-mentioned technical proposal, it is preferable that the alumina support Jing is rare-earth element modified.
In above-mentioned technical proposal, it is preferable that the specific surface area of alumina support is 3-40 rice2/ gram；It is highly preferred that aluminum oxide
The specific surface area of carrier is 6-20 rice2/ gram；Most preferably, the specific surface area of alumina support is 8-10 rice2/ gram.
In above-mentioned technical proposal, it is preferable that the pore volume of 15 nanometers -40 nanometers of the bore dia of alumina support accounts for total pore volume
75%-95%；It is highly preferred that the pore volume of 15 nanometers -40 nanometers of the bore dia of alumina support accounts for the 80%-90% of total pore volume
In above-mentioned technical proposal, the consumption of active component palladium is preferably the 0.3-1.5% of vehicle weight in terms of simple substance；Auxiliary agent zinc
Consumption is preferably the 0.1-1.0% of vehicle weight in terms of simple substance；Modifying agent rare earth element is preferably selected from least in lanthanum, cerium
Kind, consumption is preferably the 0.2-1.5% of vehicle weight in terms of simple substance；Alumina support is preferably α-Al2O3, or be preferably
α-Al2O3With θ-Al2O3Mixing crystal formation, wherein α-Al2O3With θ-Al2O3Mass ratio be 1～30.
To solve the two of above-mentioned technical problem, the technical solution used in the present invention is as follows：A kind of CO gas-phase synthesis of oxalate is urged
The preparation method of agent, comprises the following steps：
α-Al2O3Crystal formation carrier：By the steam treatment 4-8 hour of the boehmite Jing 700-800 DEG C of forming, so
It is obtained by after roasting；α-Al2O3With θ-Al2O3Mixing crystal formation carrier：By the fired prepared α of boehmite powder-
Al2O3Powder, then with boehmite powder mixed-forming by a certain percentage, the steam treatment 4-8 hour of Jing 700-800 DEG C,
Then Jing 800-950 roastings 2-6 hours are obtained；
(2) salt of rare earth metal is made into into the aqueous solution, alumina support obtained in Jing steps (1) is impregnated in the solution,
Rare earth modified alumina support is obtained after dry, roasting；Nitrate, vinegar of the salt of the rare earth metal selected from rare earth metal
At least one in hydrochlorate, sulfate or citrate；
(3) salt of the presoma of Metal Palladium and metallic zinc is made into into the aqueous solution, will be rare earth modified obtained in Jing steps (2)
Alumina support impregnates in the solution, is dried, catalyst is obtained after roasting；Halogen of the presoma of the Metal Palladium selected from palladium
At least one in compound, nitrate or acetylacetonate；The salt of metallic zinc is selected from nitrate, sulfate or the oxalates of zinc
In at least one.
Support modification agent described in the technical program：By adding appropriate rare-earth oxide in carrier surface, to reach
To carrier surface property, the purpose of pore structure is changed, so as to being conducive to carrier to the stable of active metal and disperseing；And it is described
Auxiliary agent：By adding promoter metal salt in active metal Pd maceration extracts, and form stable mixed solution so that rear
Stablize the crystal grain of Pd and the interaction force for improving Pd and carrier in continuous roasting process, to improve catalyst activity.
In above-mentioned technical proposal, in step (2), in the salt of rare earth metal is made into the aqueous solution carbon atom quantity is preferably added to
Organic acid more than 2, the pH value for making the aqueous solution is 1-5；Carbon atom quantity more than 2 organic acid be preferably selected from oxalic acid,
At least one in succinic acid, citric acid, lactic acid, terephthalic acid (TPA) or phytic acid；Preparation method also includes step (4)：
Catalyst is adopted into mixed gas reductase 12-10 under conditions of flow is for 10-150 ml/min gram catalyst, 150-400 DEG C
Hour, including inert gas, hydrogen or/and carbon monoxide in mixed gas, wherein hydrogen or/and carbon monoxide mole contains
Amount is preferably more than 10%, and inert gas is preferably selected from least one in nitrogen, carbon dioxide, helium or argon gas.
To solve the three of above-mentioned technical problem, the technical solution used in the present invention is as follows：Above-mentioned catalyst is used for into CO gas phases
Synthesis of oxalate reacts, and is 80-160 DEG C in reaction temperature with the mixed gas containing nitrites and CO as raw material, body
Product air speed is 800-6000 hours-1, reaction pressure is the condition that 0.1-1.0MPa, CO/ nitrites mol ratio is 0.5-3.0
Under, raw material generates oxalate with above-mentioned catalyst haptoreaction.
In above-mentioned technical proposal, reaction temperature is preferably 100-140 DEG C, and volume space velocity is preferably 1200-4000 hours-1, instead
Pressure is answered to be preferably 0.2-0.6MPa, CO/ nitrites mol ratios are preferably 1.5-2.5.
CO receives deployment conditions, load of active component Pd in carrier surface in catalyst with the reaction of nitrites synthesis of oxalate
The impact of the properties such as specific surface, pore volume, the Acidity of Aikalinity of body.Carrier surface can be reduced using the aluminum oxide crystal formation of high-temperature roasting
Acidity of Aikalinity, but the surface area losses of carrier are larger, are unfavorable for the dispersion of Pd.The present invention is with α-Al2O3With θ-Al2O3
Mixing crystal formation as carrier, can simultaneously reach that Acidity of Aikalinity is low, specific surface loses little effect, hence it is evident that improve catalyst performance.
Additionally, CO belongs to strong exothermal reaction with the reaction of nitrites synthesis of oxalate, quickly withdrawing for heat can effectively improve oxalic acid
Ester space-time yield simultaneously reduces the generation probability of accessory substance.Using the technology of the present invention, can effective modulation carrier pore volume, acquisition
Wide-aperture carrier, so as to effectively improve the selectivity of oxalate.
Using technical scheme, the catalyst of the present invention is anti-with methyl nitrite synthesizing dimethyl oxalate in carbon monoxide
There is higher activity and selectivity, reaction temperature is 80-160 DEG C, and volume space velocity is 800-6000 hours in answering-1, reaction
It is under conditions of 0.5-3.0, through the operating of 3000 hours, to urge that pressure is 0.1-1.0MPa, CO/ nitrites mol ratio
The space-time yield that agent performance does not have downward trend, dimethyl oxalate is more than 760g/Lh, and by-product DMC addition is less than
2.0%, and bed temperature is reasonably distributed, and can tolerate the impact of the impurity such as hydrogen, vapor, life-span length, it is easy to and control takes
Obtained preferable technique effect.
Below by embodiment, the invention will be further elaborated, but these embodiments are not anyway to the present invention's
Scope is construed as limiting.
Specific embodiment
【Embodiment 1】
By the steam treatment 6-8 hour of 750 DEG C of the boehmite Jing of forming, then 1250 DEG C of Jing roastings 3 hours,
Prepared α-Al2O3Alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.0wt%Pd+0.25wt%Zn+0.15wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum nitrate,
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, succinic acid is added in maceration extract,
PH value of solution=2 are made, is then 6.84m by specific surface area2The Al of/g2O3Carrier soaks 1 hour in maceration extract, then by this
Solids in 110 DEG C of dryings 4 hours, 400 DEG C of roastings 2 hours, then this rare earth modified carrier according to Pd and Zn
Load capacity, be configured to be soaked 6 hours in maceration extract from palladium bichloride and zinc nitrate, in 90 DEG C of dryings 3 hours, then
380 DEG C of roastings 5 hours, just make Pd-Zn-La/Al2O3Catalyst C1.Catalyst composition, property are shown in Table 1.
【Embodiment 2】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 1 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 2 hours, then 900 DEG C of Jing roastings 4 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
2.0wt%Pd+0.5wt%Zn+0.7wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum acetate, root
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, succinic acid is added in maceration extract, made
PH value of solution=2, are then 8.74m by specific surface area2The Al of/g2O3Carrier soaks 1 hour in maceration extract, then this is consolidated
Body thing in 110 DEG C of dryings 4 hours, 400 DEG C of roastings 2 hours, then this rare earth modified carrier according to Pd and Zn
Load capacity, be configured to be soaked 6 hours in maceration extract from palladium bichloride and zinc nitrate, in 90 DEG C of dryings 3 hours, then
380 DEG C of roastings 5 hours, just make Pd-Zn-La/Al2O3Catalyst C2.Catalyst composition, property are shown in Table 1.
【Embodiment 3】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 7 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 850 DEG C of Jing roastings 5 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
0.75wt%Pd+1.0wt%Zn+0.85wt%La+0.55wt%Ce/Al2O3Content prepares catalyst, comprises the following steps that：Choosing
With lanthanum nitrate and cerous sulfate, maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, in leaching
Terephthalic acid (TPA) is added in stain liquid, pH value of solution=1 is made, is then 8.79m by specific surface area2The Al of/g2O3Carrier is in dipping
Soak 3 hours in liquid, then by this solids in 80 DEG C of dryings 4 hours, then 450 DEG C of roastings 3 hours change this rare earth
Property carrier according to the load capacity of Pd and Zn, be configured to be soaked 3 hours in maceration extract from palladium nitrate and zinc sulfate,
100 DEG C of dryings 3 hours, then in 400 DEG C of roastings 6 hours, just make Pd-Zn-La-Ce/ α-Al2O3Catalyst C3.Urge
Agent composition, property are shown in Table 1.
【Embodiment 4】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 27 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 2 hours, then 940 DEG C of Jing roastings 6 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
0.3wt%Pd+0.5wt%Zn+1.5wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum nitrate, root
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, citric acid is added in maceration extract, made
PH value of solution=1.5, are then 9.88m by specific surface area2The Al of/g2O3Carrier soaks 3 hours in maceration extract, then this is consolidated
Body thing in 80 DEG C of dryings 4 hours, 480 DEG C of roastings 4 hours, then this rare earth modified carrier according to Pd's and Zn
Load capacity, is configured to be soaked 5 hours in maceration extract from palladium acetylacetonate and zinc oxalate, in 110 DEG C of dryings 5 hours, then
In 420 DEG C of roastings 5 hours, Pd-Zn-La/ α-Al are just made2O3Catalyst C4.Catalyst composition, property are shown in Table 1.
【Embodiment 5】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 30 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 820 DEG C of Jing roastings 5 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
0.3wt%Pd+0.7wt%Zn+0.7wt%La+0.7wt%Ce/Al2O3Content prepares catalyst, comprises the following steps that：From lemon
Lemon acid lanthanum and cerous nitrate, according to load capacity maceration extract is prepared, in order to control modification of the rare earth metal to carrier surface, in dipping
Phytic acid is added in liquid, pH value of solution=1.3 are made, is then 9.96m by specific surface area2The Al of/g2O3Carrier soaks in maceration extract
3 hours, then by this solids in 140 DEG C of dryings 12 hours, 500 DEG C of roastings 4 hours were then rare earth modified this
Carrier is configured to be soaked 5 hours in maceration extract, at 100 DEG C according to the load capacity of Pd and Zn from palladium nitrate and zinc nitrate
It is dried 5 hours, then in 450 DEG C of roastings 6 hours, just makes Pd-Zn-La-Ce/ α-Al2O3Catalyst C5.Catalyst
Composition, property are shown in Table 1.
【Embodiment 6】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 20 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 950 DEG C of Jing roastings 6 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.2wt%Pd+0.5wt%Zn+0.3wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum sulfate, root
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, lactic acid is added in maceration extract, made molten
Liquid pH=2.8, is then 9.17m by specific surface area2The Al of/g2O3Carrier soaks 2 hours in maceration extract, then by this solid
Thing in 120 DEG C of dryings 10 hours, 480 DEG C of roastings 4 hours, then this rare earth modified carrier according to Pd's and Zn
Load capacity, is configured to be soaked 7 hours in maceration extract, in 110 DEG C of dryings 5 hours, then at 450 DEG C from palladium nitrate and zinc sulfate
Roasting 6 hours, just makes Pd-Zn-La/ α-Al2O3Catalyst C6.Catalyst composition, property are shown in Table 1.
【Embodiment 7】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 12 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 800 DEG C of Jing roastings 5 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.5wt%Pd+0.3wt%Zn+1.2wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum acetate, root
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, lactic acid and phytic acid is added in maceration extract,
PH value of solution=3.5 are made, is then 9.04m by specific surface area2The Al of/g2O3Carrier soaks 2 hours in maceration extract, then by this
Solids in 130 DEG C of dryings 9 hours, 520 DEG C of roastings 4 hours, then this rare earth modified carrier according to Pd and Zn
Load capacity, be configured to be soaked 6 hours in maceration extract from palladium nitrate and zinc oxalate, in 100 DEG C of dryings 4 hours, then
420 DEG C of roastings 7 hours, just make Pd-Zn-La/Al2O3Catalyst C7.Catalyst composition, property are shown in Table 1.
【Embodiment 8】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 3 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 850 DEG C of Jing roastings 3 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.0wt%Pd+0.25wt%Zn+0.15wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum nitrate,
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, succinic acid is added in maceration extract,
PH value of solution=2 are made, is then 8.21m by specific surface area2The Al of/g2O3Carrier soaks 1 hour in maceration extract, then this is consolidated
Body thing in 110 DEG C of dryings 4 hours, 400 DEG C of roastings 2 hours, then this rare earth modified carrier according to Pd and Zn
Load capacity, be configured to be soaked 6 hours in maceration extract from palladium bichloride and zinc nitrate, in 90 DEG C of dryings 3 hours, then
380 DEG C of roastings 5 hours, just make Pd-Zn-La/Al2O3Catalyst C8.Catalyst composition, property are shown in Table 1.
【Embodiment 9】
By the steam treatment 7 hours of 750 DEG C of the boehmite Jing of forming, then 1250 DEG C of Jing roastings 3 hours, system
Obtain α-Al2O3Alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.0wt%Pd+0.25wt%Zn+0.15wt%La/Al2O3Content prepares catalyst, comprises the following steps that：According to Pd, Zn and
The load capacity of La selects palladium bichloride, zinc nitrate and lanthanum nitrate, prepares maceration extract, and succinic acid is added in maceration extract, makes solution
PH=2, is then 6.83m by specific surface area2The Al of/g2O3Carrier soaks 4 hours in maceration extract, then this solids is existed
110 DEG C of dryings 4 hours, 400 DEG C of roastings 2 hours, just make Pd-Zn-La/Al2O3Catalyst C9.Catalyst composition,
Property is shown in Table 1.
【Embodiment 10】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 1 with boehmite powder：2
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 880 DEG C of Jing roastings 4 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.5wt%Pd+0.3wt%Zn+1.2wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum acetate, root
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, lactic acid and phytic acid is added in maceration extract,
PH value of solution=3.0 are made, is then 8.32m by specific surface area2The Al of/g2O3Carrier soaks 3 hours in maceration extract, then by this
Solids in 110 DEG C of dryings 7 hours, 500 DEG C of roastings 4 hours, then this rare earth modified carrier according to Pd and Zn
Load capacity, be configured to be soaked 2 hours in maceration extract from palladium nitrate and zinc oxalate, in 100 DEG C of dryings 4 hours, then
450 DEG C of roastings 7 hours, just make Pd-Zn-La/Al2O3Catalyst C10.Catalyst composition, property are shown in Table 1.
【Embodiment 11】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 40 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 800 DEG C of Jing roastings 4 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.5wt%Pd+0.3wt%Zn+1.2wt%La/Al2O3Content prepares catalyst, comprises the following steps that：From lanthanum acetate, root
Maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface, lactic acid and phytic acid is added in maceration extract,
PH value of solution=3.0 are made, is then 7.75m by specific surface area2The Al of/g2O3Carrier soaks 3 hours in maceration extract, then by this
Solids in 100 DEG C of dryings 3 hours, 480 DEG C of roastings 4 hours, then this rare earth modified carrier according to Pd and Zn
Load capacity, be configured to be soaked 2 hours in maceration extract from palladium nitrate and zinc oxalate, in 110 DEG C of dryings 4 hours, then
450 DEG C of roastings 4 hours, just make Pd-Zn-La/Al2O3Catalyst C11.Catalyst composition, property are shown in Table 1.
【Embodiment 12】
By 1250 DEG C of boehmite powder Jing roastings 4 hours, α-Al are obtained2O3Powder, then press 12 with boehmite powder：1
Mass ratio mixed-forming, the steam treatment that 750 DEG C of Jing 3 hours, then 800 DEG C of Jing roastings 5 hours are obtained α-Al2O3
With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed, in terms of metal simple-substance (as follows), is pressed
1.5wt%Pd+0.05wt%K/Al2O3Content prepares catalyst, comprises the following steps that：From potassium carbonate and palladium, according to
Load capacity prepares maceration extract, and lactic acid and phytic acid are added in maceration extract, make pH value of solution=3.5, be then by specific surface area
9.04m2The Al of/g2O3Carrier soaks 5 hours in maceration extract, in 100 DEG C of dryings 4 hours then little in 420 DEG C of roastings 7
When, just make Pd-K/Al2O3Catalyst C12.Catalyst composition, property are shown in Table 1.
【Comparative example 1】
It is obtained using the methods described of embodiment in patent CN95116136.9 4 and compares catalyst, is designated as D1.Catalyst composition,
Property is shown in Table 1.
【Comparative example 2】
By boehmite powder in 750 DEG C of roastings 4 hours, θ-Al are obtained2O3, by boehmite powder in 1250 DEG C of roastings
4 hours, α-Al are obtained2O3Powder.Again by θ-Al2O3With α-Al2O3Powder presses 1：After the shaping of 1 mass ratio mechanical mixture
750 DEG C of Jing roastings 4 hours, are obtained α-Al2O3With θ-Al2O3Mixed crystal alumina support.100g alumina supports are weighed,
In terms of metal simple-substance (as follows), by 2.0wt%Pd+0.5wt%Zn+0.7wt%La/Al2O3Content prepares catalyst, tool
Body step is as follows：From lanthanum acetate, maceration extract is prepared according to load capacity, in order to control modification of the rare earth metal to carrier surface,
Succinic acid is added in maceration extract, pH value of solution=2 are made, is then 7.57m by specific surface area2The Al of/g2O3Carrier is in maceration extract
Middle immersion 1 hour, then by this solids in 110 DEG C of dryings 4 hours, 400 DEG C of roastings 2 hours are then rare earth modified this
Carrier according to the load capacity of Pd and Zn, be configured to be soaked 6 hours in maceration extract from palladium bichloride and zinc nitrate,
90 DEG C of dryings 3 hours, then in 380 DEG C of roastings 5 hours, just make Pd-Zn-La/Al2O3Catalyst D2.Catalyst group
1 is shown in Table into, property.
【Embodiment 13】
This example demonstrates that embodiment 1-11 gained catalyst reacts in carbon monoxide and methyl nitrite synthesizing dimethyl oxalate
In application.
Take each 40 grams of embodiment of the present invention 1-11 gained catalyst C1-C11 and load the stainless steel reaction pipe that internal diameter is 20 millimeters
In, adopt mixed gas to reduce 4 hours under conditions of flow is for 50 ml/min gram catalyst, 240 DEG C, mixed gas
In comprising the hydrogen, 15% carbon monoxide and surplus nitrogen that molar content is 40%.Carbon monoxide is passed through after reduction with Asia
Methyl nitrate carries out reaction examination.In 128 DEG C of reaction temperature, reaction volume air speed is 2800h to catalyst-1, reaction pressure is
The mol ratio of 0.25MPa, CO/ methyl nitrite is 2:Reacted under conditions of 1.The result of reaction 200h is listed in table 2.
【Comparative example 3】
Take 40 grams of comparative example 1-2 gained catalyst and load the stainless steel reaction pipe that internal diameter is 20 millimeters, adopt and embodiment 1-11
Same raw material and condition carries out reaction examination.The result of reaction 200h is listed in table 2.
【Embodiment 14】
This example demonstrates that the gained catalyst of embodiment 5 is in the reaction of carbon monoxide and methyl nitrite synthesizing dimethyl oxalate
Change the result of the test of process conditions.
Take 40 grams of 5 gained catalyst of the embodiment of the present invention to be fitted in the stainless steel reaction pipe that internal diameter is 20 millimeters.Using mixing
Gas is 140 ml/min gram catalyst, reduces 8 hours under conditions of 190 DEG C, contains comprising mole in mixed gas in flow
Measure the hydrogen and surplus nitrogen for 70%.Carbon monoxide and methyl nitrite are passed through after reduction, are changed process conditions and is tried
Test.The result of reaction 200h is listed in table 3.
【Embodiment 15】
This example demonstrates that the gained catalyst of embodiment 6 result of the test of 6000 hours in hydrogenation of oxalate for preparing ethylene glycol.
Take 40 grams of 6 gained catalyst of the embodiment of the present invention to be fitted in the stainless steel reaction pipe that internal diameter is 20 millimeters.Using mixing
Gas is 100 ml/min gram catalyst, reduces 5 hours under conditions of 180 DEG C, contains comprising mole in mixed gas in flow
Measure the hydrogen and surplus nitrogen for 90%.Carbon monoxide and methyl nitrite are passed through after reduction, are 0.35MPa in pressure
Under, temperature be 135 DEG C, air speed be 4000h-1, the mol ratio of CO/ methyl nitrites is to be reacted under conditions of 1.8.
The result of reaction 6000h is listed in table 4.
【Comparative example 4】
Take 40 grams of 1 gained catalyst of comparative example and load the stainless steel reaction pipe that internal diameter is 20 millimeters, using same with embodiment 9
The raw material and condition of sample carries out reaction examination.Reaction result is listed in table 4.
Table 1
Table 2
Table 3
Table 4
Claims (10)
1. a kind of catalyst of CO gas-phase synthesis of oxalate, including carrier, active component, auxiliary agent and/or modifying agent, with
Percentage by weight meter, catalyst includes following component：
A) with palladium as active component, 0.1-4.0% of the consumption as vehicle weight is counted with simple substance；
B) with zinc as auxiliary agent, 0.05-2.0% of the consumption as vehicle weight is counted with simple substance；
C) with rare earth element as auxiliary agent or modifying agent, 0.1-3.0% of the consumption as vehicle weight is counted with simple substance；
D) with least one of aluminum oxide or silica as carrier.
2. the catalyst of CO gas-phase synthesis of oxalate according to claim 1, it is characterised in that the use of active component palladium
Amount is calculated as the 0.3-1.5% of vehicle weight with simple substance.
3. the catalyst of CO gas-phase synthesis of oxalate according to claim 1, it is characterised in that the consumption of auxiliary agent zinc with
Simple substance is calculated as the 0.1-1.0% of vehicle weight.
4. the catalyst of CO gas-phase synthesis of oxalate according to claim 1, it is characterised in that auxiliary agent or modifying agent are dilute
At least one of the earth elements in lanthanum, cerium, with simple substance 0.2-1.5% of the consumption as vehicle weight is counted.
5. the catalyst of CO gas-phase synthesis of oxalate according to claim 1, it is characterised in that the alumina support
The pore volume that 15 nanometers -40 nanometers of bore dia accounts for the 75%-95% of total pore volume.
6. the catalyst of CO gas-phase synthesis of oxalate according to claim 5, it is characterised in that the alumina support
The pore volume that 15 nanometers -40 nanometers of bore dia accounts for the 80%-90% of total pore volume.
7. the catalyst of CO gas-phase synthesis of oxalate according to claim 1, it is characterised in that the alumina support
For α-Al2O3；Or alumina support is α-Al2O3With θ-Al2O3Mixing crystal formation, wherein α-Al2O3With θ-
Al2O3Mass ratio be 1～30.
8. the preparation method of CO catalyst for synthesizing oxalic ester by gas-phase described in any one of claim 1～7, comprises the following steps：
(1)α-Al2O3Crystal formation carrier：By the steam treatment 4-8 hour of the boehmite Jing 700-800 DEG C of forming,
Then it is fired rear prepared；α-Al2O3With θ-Al2O3Mixing crystal formation carrier：By the fired prepared α of boehmite powder
-Al2O3Powder, then with boehmite powder mixed-forming by a certain percentage, the steam treatment 4-8 hour of Jing 700-800 DEG C,
Then Jing 800-950 DEG C roastings 2-6 hours are obtained；
(2) salt of rare earth metal is made into into the aqueous solution, alumina support obtained in Jing steps (1) is impregnated in the solution,
Rare earth modified alumina support is obtained after dry, roasting；Nitrate, vinegar of the salt of the rare earth metal selected from rare earth metal
At least one in hydrochlorate, sulfate or citrate；
(3) salt of the presoma of Metal Palladium and metallic zinc is made into into the aqueous solution, will be rare earth modified obtained in Jing steps (2)
Alumina support impregnates in the solution, is dried, catalyst is obtained after roasting；Halogen of the presoma of the Metal Palladium selected from palladium
At least one in compound, nitrate or acetylacetonate；The salt of metallic zinc is selected from nitrate, sulfate or the oxalates of zinc
In at least one.
9. a kind of method of CO catalyst for synthesizing oxalic ester by gas-phase, with the mixed gas containing nitrites and CO as raw material,
It it is 80-160 DEG C in reaction temperature, volume space velocity is 800-6000 hours-1, reaction pressure is 0.1-1.0MPa, CO/ nitrous
Acid esters mol ratio is that raw material is contacted with catalyst described in any one of claim 1～7 under conditions of 0.5-3.0, and reaction is generated
Oxalate.
10. the method for CO catalyst for synthesizing oxalic ester by gas-phase according to claim 9, it is characterised in that reaction temperature is
100-140 DEG C, volume space velocity is 1200-4000 hours-1, reaction pressure is 0.2-0.6MPa, CO/ nitrites mol ratios
For 1.5-2.5.
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