CN105396584B - CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage - Google Patents
CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage Download PDFInfo
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Abstract
CO couplings catalyst for synthesizing oxalic ester, preparation method and its usage, the present invention relates to a kind of catalyst of carbon monoxide vapor- phase synthesis oxalate, mainly solving the technical problems that it is low catalyst activity to be in the prior art present, the nitrous acid ester conversion ratio during carbon monoxide vapor- phase synthesis oxalate and low oxalate space-time yield the problem of.The present invention is by using by weight percentage, including following components：1) 0.05~2.5wt% palladiums；2) 0.06~3wt% lanthanide series metals or its oxide；3) 94.5~99.8wt% carriers, carrier are selected from least one of aluminum oxide, silica or molecular sieve；Wherein, palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are the technical scheme of 0.8~4.5 catalyst, preferably solve the problem, available in carbon monoxide vapor- phase synthesis oxalate industrial production.
Description
Technical field
The present invention relates to a kind of catalyst for carbon monoxide vapor- phase synthesis oxalate, particularly for carbon monoxide gas
It is combined to the catalyst of dimethyl oxalate or diethy-aceto oxalate.
Background technology
Oxalate is a kind of important Organic Chemicals, is largely used to fine chemistry industry and prepares various dyestuffs, medicine, molten
Agent, extractant and various intermediates.In addition, oxalic acid ester through hydrogenation can prepare highly important industrial chemicals ethylene glycol, this route
The method that may replace the higher petroleum path production ethylene glycol of current cost.
Traditional oxalate production line has starch nitric acid oxidation method, cellulose alkali fusion, sodium formate method, the step of ethylene glycol one
Oxidizing process, oxidation of propylene and oxalic acid alcohol esterification reaction method, but above-mentioned traditional handicraft is present that cost is high, energy consumption is big, it is seriously polluted,
Raw material utilizes the shortcomings of unreasonable.So have to look for the friendly process route of a cost low environment.Nineteen sixty-five American Association
Oil company be found that carbon monoxide, alcohol and oxygen palladium chtalyst effect under can direct synthesis of oxalate, Ube is emerging since then
Production company and ARCO companies of the U.S. have carried out research and development in this field in succession, and Ube Industries Ltd. just proposes within 1977
Normal pressure gas-phase synthesis of oxalate technology, using Pd/A12O3 as catalyst, under the conditions of 80~150 DEG C of temperature, pressure 0.5MPa, grass
The yield 98% of dimethyl phthalate.Nitrogen oxide in methanol and tail gas uses dioxygen oxidation, synthesis methyl nitrite circulation at high temperature
Use.
China is a coal resources relative abundance, and carbon monoxide source is sufficient, is coupled and synthesized using carbon monoxide gas phase
The route of oxalate repeated hydrogenation preparing ethylene glycol tallies with the national condition, and is an economically viable technology path.It is so domestic many
Enterprise and research institution have made substantial amounts of work to this field.It is used for for example, patent 200810035248.6 discloses one kind
Catalyst of oxalic acid Lipase absobed and its preparation method and application, the catalyst using Alpha-alumina as carrier, comprising 0.01~
1wt% active constituent Pd, 0.01~0.5wt% auxiliary agent Ir, the catalyst oxalate space-time yield are 750g/L.cat.Specially
Sharp CN200710061392 discloses catalyst of CO low-voltage gas-phase synthesizing of oxalic ester and preparation method thereof, and the catalyst is with metal
Palladium is main active constituent, and using titanium and cerium as co-catalyst, its carrier is that modified Alpha-alumina is carrier, the catalyst oxalic acid two
The space-time yield of methyl esters is 700g/L.cat.H.But such research report is mostly concentrated on to catalyst formulation and carrier structure
Improvement in terms of, the space-time yield for developing catalyst oxalate also need to be improved.
Because CO catalyst for synthesizing oxalic ester by gas-phase is the catalyst of a structure sensitive, the height of the catalyst activity is not
It is only relevant with catalyst formulation, carrier structure, also and activity over catalysts component palladium the suction type to raw material carbon monoxide
It is relevant, improve the conversion ratio that active component palladium in catalyst is advantageous to improve nitrous acid ester to the bridged adsorption intensity of carbon monoxide
With the space-time yield of oxalate.
The content of the invention
The technical problems to be solved by the invention are low, the carbon monoxide vapor- phase synthesis that catalyst activity in the prior art be present
A kind of nitrous acid ester conversion ratio and the problem of low oxalate space-time yield during oxalate, there is provided new CO coupling synthesis of oxalic acid
Ester catalyst.The two of the technical problems to be solved by the invention are to provide a kind of system of new CO coupling catalyst for synthesizing oxalic ester
Preparation Method, being coupled using catalyst prepared by this method in CO during synthesis of oxalate has methyl nitrite conversion ratio and grass
The characteristics of acid esters space-time yield is high.The three of the technical problems to be solved by the invention are to provide a kind of with solving one of technical problem
Corresponding catalyst is used for the method for CO coupling synthesis of oxalate.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：One kind is used for CO coupling synthesis of oxalate
Catalyst, by weight percentage, including following components：1) 0.05~2.5wt% palladiums；2) 0.06~3wt% lanthanide series metals or
Its oxide；3) 94.5~99.8wt% carriers, carrier are selected from least one of aluminum oxide, silica or molecular sieve；Wherein,
Palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are 0.8~4.5.
In above-mentioned technical proposal, by weight percentage, component 2) content be preferably 0.1~2wt%.
In above-mentioned technical proposal, palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are preferably in catalyst
1~4.5, more preferably 1.5~4.5.
In above-mentioned technical proposal, in catalyst the average grain diameter of palladium crystal grain be 3~21 nanometers, preferably 3~12.
To solve the two of above-mentioned technical problem, the preparation method of heretofore described catalyst, mainly include the following steps that：
Comprise the following steps：
A) soluble-salt of active constituent palladium and auxiliary agent is dissolved into the water containing anion surfactant, it is to be dissolved
After the completion of adjust pH value of solution be 1.5~6.5, obtain maceration extract I；
B) maceration extract I is impregnated or be sprayed at carrier, obtain catalyst precarsor；
C) by catalyst precarsor aging, drying, roasting, reduction in atmosphere, required catalyst is produced.
Content is preferably 0.02~0.6wt% in anion surfactant water described in above-mentioned technical proposal.
PH described in above-mentioned technical proposal is 3~6
To solve the three of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of carbon monoxide vapor- phase synthesis
The method of oxalate, in 110~170 DEG C, 0~1MPa of reaction pressure of reaction temperature, raw material carbon monoxide and nitrous acid ester rub
, than being 1~4, volume space velocity is 800~4000h for you-1Under the conditions of with catalyst haptoreaction described in above-mentioned technical proposal, generation
Effluent containing oxalate.
Absorption of the active constituent palladium to carbon monoxide in palladium catalyst can be divided into two ways, and one kind is inhaled for bridge-type
Attached, another kind adsorbs for wire type.And in the reaction of carbon monoxide vapor- phase synthesis producing oxalic ester, only deposited in a manner of bridged adsorption
Carbon monoxide could participate in reacting, with methyl nitrite generate oxalate.So active constituent palladium in catalyst is ensured
In the case of reaching certain decentralization, the ratio for improving palladium bridged adsorption carbon monoxide in catalyst is advantageous to improve nitrous acid ester
Conversion ratio and oxalate space-time yield.
The present invention effectively adjusts catalysis by adding anion surfactant in maceration extract and adjusting the method for pH value
The decentralization of palladium and the suction type to carbon monoxide in agent, Gu compared with prior art, catalyst metals palladium point of the invention
Dissipate good, and palladium is high to the bridged adsorption ratio of carbon monoxide, be advantageous to improve in catalyst the utilization rate of active constituent palladium and
Catalytic activity.Using the inventive method, nitrous acid ester conversion ratio can reach 89%, and oxalate space-time yield can reach 1150g/
L.H-1, achieve preferable technique effect.
In the inventive method, using following method of testing：
1) catalytic component is determined by ICP.
2) palladium crystal grain average grain diameter：The particle diameter of palladium crystal grain is measured by x-ray diffractometer (XRD).
3) palladium is to carbon monoxide determining adsorption：Catalyst is ground into the powder below 500 mesh, takes 20mg to be pressed into diameter
The good thin slice of 12mm, thickness 0.1mm translucency, is placed in In-situ Infrared pond.200 degree of reductase 12 hours of hydrogen are first used, are reduced
By sample cell pumping high vacuum after end, then CO gas is passed through, allows Catalyst Adsorption saturation, utilize infrared test instrument to survey
Determine palladium in catalyst and peak intensity is adsorbed to carbon monoxide bridge-type and wire type.
Below by specific embodiment, the invention will be further described.
Embodiment
【Embodiment 1】
Take 60g alumina supports.0.3g palladium bichlorides and 0.12g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.1% fatty alcohol polyoxy
In the deionized water of ethene ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.0 after dissolving.Maceration extract I is slow
Slowly it is added in carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.Catalyst precarsor is old in atmosphere
80 DEG C of drying after changing 20 hours, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen
Reduction obtains carbon monoxide vapor- phase synthesis oxalate catalyst cat-1A after 8 hours.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 2】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.1% aliphatic alcohol polyethenoxy
In the deionized water of ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.0 after dissolving.Maceration extract I is slowly added
Enter into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging 20 in atmosphere
80 DEG C of drying after hour, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen reducings 8
Carbon monoxide vapor- phase synthesis oxalate catalyst cat-2A is obtained after hour.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 3】
Take 60g alumina supports.0.3g palladium bichlorides and 0.56g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.1% fatty alcohol polyoxy
In the deionized water of ethene ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.0 after dissolving.Maceration extract I is slow
Slowly it is added in carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.Catalyst precarsor is old in atmosphere
80 DEG C of drying after changing 20 hours, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen
Reduction obtains carbon monoxide vapor- phase synthesis oxalate catalyst cat-3A after 8 hours.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 4】
Take 60g silica supports.0.05g palladium bichlorides and 3.7g cerous nitrates is taken to be dissolved in 45ml and contain 0.1% fatty alcohol polyoxy
In the deionized water of ethene ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.0 after dissolving.Maceration extract I is slow
Slowly it is added in carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.Catalyst precarsor is old in atmosphere
80 DEG C of drying after changing 20 hours, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen
Reduction obtains carbon monoxide vapor- phase synthesis oxalate catalyst cat-4A after 8 hours.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 5】
Take 60g 4A type molecular sieve carriers.0.1g palladium bichlorides and 1.3g samaric nitrates is taken to be dissolved in 35ml and contain 0.1% lauryl
In the deionized water of sodium sulphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.0 after dissolving.Maceration extract I is slowly added into
Into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor, aging 20 is small in atmosphere
When after 80 DEG C of drying, then be put in Muffle furnace 450 DEG C of roastings, placing into reactor internal program, to be warming up to 300 DEG C of hydrogen reducings 8 small
When after obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-5A.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 6】
Take 60g ZSM-5 molecular sieve carriers.2.5g palladium bichlorides, 0.42g praseodymium nitrates and 0.67g sodium nitrate is taken to be dissolved in 35ml
In deionized water containing 0.1% aliphatic alcohol polyoxyvinethene phosphate, addition sodium carbonate regulation pH is soaked for 4.0 after dissolving
Stain liquid I.Maceration extract I is slowly added in carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.It will urge
The 80 DEG C of drying after aging 20 hours in atmosphere of agent precursor, then 450 DEG C of roastings in Muffle furnace are put in, place into journey in reactor
Sequence is warming up to 300 DEG C of hydrogen reducings and carbon monoxide vapor- phase synthesis oxalate catalyst cat-6A is obtained after 8 hours.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 7】
Take 60g alumina supports.1g palladium bichlorides and 0.19g neodymium nitrates is taken to be dissolved in 30ml and contain 0.1% detergent alkylate sulphur
In the deionized water of sour sodium, addition sodium carbonate regulation pH obtains maceration extract I for 4.0 after dissolving.Maceration extract I is slowly added to
In carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging 20 hours in atmosphere
80 DEG C of drying afterwards, then be put in Muffle furnace 450 DEG C of roastings, place into reactor internal program and be warming up to 300 DEG C of hydrogen reducings 8 hours
After obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-7A.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 8】
Take 60g silica supports.2.5g palladium bichlorides and 1.1g lanthanum nitrates is taken to be dissolved in 45ml and gone containing 0.1% odium stearate
In ionized water, addition sodium carbonate regulation pH obtains maceration extract I for 4.0 after dissolving.Maceration extract I is slowly added in carrier,
And stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By 80 DEG C after catalyst precarsor in atmosphere aging 20 hours
Drying, then be put in Muffle furnace 450 DEG C of roastings, places into reactor internal program and is warming up to 300 DEG C of hydrogen reducings and obtained after 8 hours
Carbon monoxide vapor- phase synthesis oxalate catalyst cat-8A.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 9】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.1% aliphatic alcohol polyethenoxy
In the deionized water of ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 1.5 after dissolving.Maceration extract I is slowly added
Enter into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging 20 in atmosphere
80 DEG C of drying after hour, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen reducings 8
Carbon monoxide vapor- phase synthesis oxalate catalyst cat-10A is obtained after hour.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 10】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.1% aliphatic alcohol polyethenoxy
In the deionized water of ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 6.5 after dissolving.Maceration extract I is slowly added
Enter into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging 20 in atmosphere
80 DEG C of drying after hour, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen reducings 8
Carbon monoxide vapor- phase synthesis oxalate catalyst cat-10A is obtained after hour.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 11】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.1% aliphatic alcohol polyethenoxy
In the deionized water of ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 3 after dissolving.Maceration extract I is slowly added into
Into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor, aging 20 is small in atmosphere
When after 80 DEG C of drying, then be put in Muffle furnace 450 DEG C of roastings, placing into reactor internal program, to be warming up to 300 DEG C of hydrogen reducings 8 small
When after obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-11A.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 12】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.1% aliphatic alcohol polyethenoxy
In the deionized water of ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 6 after dissolving.Maceration extract I is slowly added into
Into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor, aging 20 is small in atmosphere
When after 80 DEG C of drying, then be put in Muffle furnace 450 DEG C of roastings, placing into reactor internal program, to be warming up to 300 DEG C of hydrogen reducings 8 small
When after obtain carbon monoxide vapor- phase synthesis oxalate catalyst cat-12A.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 13】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.02% fatty alcohol polyoxy second
In the deionized water of alkene ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.5 after dissolving.By maceration extract I slowly
It is added in carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging in atmosphere
80 DEG C of drying after 20 hours, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen also
Carbon monoxide vapor- phase synthesis oxalate catalyst cat-13A is obtained after former 8 hours.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 14】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.3% aliphatic alcohol polyethenoxy
In the deionized water of ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.5 after dissolving.Maceration extract I is slowly added
Enter into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging 20 in atmosphere
80 DEG C of drying after hour, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen reducings 8
Carbon monoxide vapor- phase synthesis oxalate catalyst cat-14A is obtained after hour.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Embodiment 15】
Take 60g alumina supports.0.3g palladium bichlorides and 1g lanthanum nitrates is taken to be dissolved in 30ml and contain 0.6% aliphatic alcohol polyethenoxy
In the deionized water of ether phosphate, addition sodium carbonate regulation pH obtains maceration extract I for 4.5 after dissolving.Maceration extract I is slowly added
Enter into carrier, and stirring carrier makes solution dipping uniform, and catalyst precarsor is made.By catalyst precarsor aging 20 in atmosphere
80 DEG C of drying after hour, then 450 DEG C of roastings in Muffle furnace are put in, place into reactor internal program and be warming up to 300 DEG C of hydrogen reducings 8
Carbon monoxide vapor- phase synthesis oxalate catalyst cat-15A is obtained after hour.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Comparative example 1】
Formula according to embodiment 2 is：60g alumina supports, 0.3g palladium bichlorides and 1g lanthanum nitrates are taken according to patent
200810035248.6 method prepare catalyst cat1B.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Comparative example 2】
Formula according to embodiment 2 is：60g alumina supports, 0.3g palladium bichlorides and 1g lanthanum nitrates are taken, then by patent
200810114383.X method carbon monoxide vapor- phase synthesis oxalate catalyst cat-2B is prepared.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Comparative example 3】
According to【Embodiment 1】Preparation method, do not add lanthanide Group species simply, prepare catalyst cat-3B.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Comparative example 4】
According to【Embodiment 2】Preparation method, anion surfactant is not added in maceration extract simply, prepares and urges
Agent cat-4B.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
【Comparative example 5】
According to【Embodiment 2】Preparation method, do not adjust the pH value (pH value 0.8) of maceration extract simply, prepare catalysis
Agent cat-5B.
Analysis is tested palladium on constituent content, palladium crystal grain average grain diameter and the catalyst of catalyst and, to carbon monoxide absorption, surveyed
Test result is shown in Table 1.
Table 1
Wherein ACO bridge-types/ACO wire typesFor palladium bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio
【Embodiment 16】
This example demonstrates that the gained catalyst of embodiment 1~15 has been coupled answering in synthesizing dimethyl oxalate reaction in CO
With.
The gained catalyst of the embodiment of the present invention 1~15 is taken to carry out reaction examination, in 140 DEG C of reaction temperature, reaction pressure is
0.2MPa, CO are 1.5 with methyl nitrite mol ratio, and volume space velocity is that CO coupling synthesis grass is carried out under conditions of 2500 hours -1
Dimethyl phthalate is reacted, and product is condensed by methanol absorption after reaction, gas-liquid separation, does sampling analysis to gas phase and liquid phase respectively.Instead
2 should be the results are shown in Table.
【Comparative example 6】
Take the gained catalyst of comparative example 1~5 to carry out reaction examination, using with the identical reducing condition raw material of embodiment 16 and
Reaction condition.Reaction result is shown in Table 2.
Table 2
The catalyst of the present invention is in carbon monoxide vapor- phase synthesis oxalic acid it can be seen from test result and synthetic reaction effect
In ester reaction, to nitrous acid ester conversion ratio, oxalate space-time yield apparently higher than reference sample, have it is obvious it is progressive with it is excellent
Gesture.
【Embodiment 17】
This example demonstrates that the gained catalyst of embodiment 2 changes in the reaction of carbon monoxide gas phase coupling synthesis of oxalate
The result of the test of process conditions, reaction condition and the results are shown in Table 3.
Table 3
Claims (9)
1. one kind is used for CO coupling catalyst for synthesizing oxalic ester, by weight percentage, composed of the following components：0.05 1)~
2.5wt% palladiums；2) 0.06~3wt% lanthanide series metals or its oxide；3) 94.5~99.8wt% carriers, carrier are selected from oxidation
At least one of aluminium, silica or molecular sieve；Wherein, palladium bridged adsorption carbon monoxide and the oxidation of wire type absorption one in catalyst
Carbon ratio example is 0.8~4.5；
The preparation of the catalyst, comprises the following steps：
A) soluble-salt of active constituent palladium and auxiliary agent is dissolved into the water containing anion surfactant, completion to be dissolved
It is 1.5~6.5 to adjust pH value of solution afterwards, obtains maceration extract I；
B) maceration extract I is impregnated or be sprayed at carrier, obtain catalyst precarsor；
C) by catalyst precarsor aging, drying, roasting, reduction in atmosphere, required catalyst is produced.
2. it is used for CO coupling catalyst for synthesizing oxalic ester according to claim 1, it is characterised in that by weight percentage, group
It is 0.1~2wt% to divide content 2).
3. it is used for CO coupling catalyst for synthesizing oxalic ester according to claim 1, it is characterised in that palladium bridge-type is inhaled in catalyst
Attached carbon monoxide and wire type sorbing carbon monoxide ratio are 1~4.5.
4. it is used for CO coupling catalyst for synthesizing oxalic ester according to claim 3, it is characterised in that palladium catalyst in catalyst
Bridged adsorption carbon monoxide and wire type sorbing carbon monoxide ratio are 1.5~4.5.
5. it is used for CO catalyst for synthesizing oxalic ester by gas-phase according to claim 1, it is characterised in that palladium crystal grain in catalyst
Average grain diameter is nanometer 3~21.
6. it is used for CO catalyst for synthesizing oxalic ester by gas-phase according to claim 5, it is characterised in that palladium crystal grain in catalyst
Average grain diameter is nanometer 3~12.
7. according to claim 1 be used for CO catalyst for synthesizing oxalic ester by gas-phase, it is characterised in that the anionic surface
Activating agent content in water is 0.02~0.6wt%.
8. according to claim 1 be used for CO catalyst for synthesizing oxalic ester by gas-phase, it is characterised in that maceration extract pH is 3~6.
9. a kind of method of carbon monoxide vapor- phase synthesis oxalate, in 110~170 DEG C, 0~1MPa of reaction pressure of reaction temperature,
The mol ratio of raw material carbon monoxide and nitrous acid ester is 1~4, and volume space velocity is 800~4000h-1Under the conditions of with claim 1~
Any one of 8 catalyst haptoreactions, generate the effluent containing oxalate.
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