CN105435783B - The catalyst of CO gas phase coupling synthesis of oxalate - Google Patents
The catalyst of CO gas phase coupling synthesis of oxalate Download PDFInfo
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- CN105435783B CN105435783B CN201410429423.5A CN201410429423A CN105435783B CN 105435783 B CN105435783 B CN 105435783B CN 201410429423 A CN201410429423 A CN 201410429423A CN 105435783 B CN105435783 B CN 105435783B
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Abstract
The present invention relates to a kind of catalyst of CO gas phase couplings synthesis of oxalate, mainly solve the problems, such as it is that catalyst activity to be in the prior art present low, nitrous acid ester conversion ratio and the problem of low oxalate space-time yield during carbon monoxide vapor- phase synthesis oxalate.The present invention is by using by weight percentage, including following component：1) 0.03~3wt% palladiums；2) 0.05~4wt% lanthanide series metals or its oxide；3) at least one of races of 0~3wt% the VIIIth metal or its oxide；4) 90~99.8wt% is selected from the technical scheme of at least one of aluminum oxide, the silica or molecular sieve catalyst of carrier, the problem is preferably resolved, in the industrial production available for CO gas phase coupling synthesis of oxalate.
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, with Pd/A12O3For 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, but the space-time in oxalate is still relatively low.For example, patent
200810035248.6 disclose a kind of catalyst for oxalic acid Lipase absobed and its preparation method and application, the catalyst with
Alpha-alumina is carrier, the auxiliary agent Ir of active constituent Pd, 0.01~0.5wt% comprising 0.01~1wt%, the catalyst oxalic acid
Ester space-time yield is 750g/L.cat.Patent CN200710061392 disclose CO low-voltage gas-phase synthesizing of oxalic ester catalyst and
Its preparation method, the catalyst is using Metal Palladium as main active constituent, and using titanium and cerium as co-catalyst, its carrier is modified α-oxygen
Change aluminium is carrier, and the space-time yield of the catalyst dimethyl oxalate is 700g/L.cat.H.
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 gas phase couplings synthesis
Oxalic acid ester catalyst.The catalyst has nitrous acid ester conversion ratio and the production of oxalate space-time in the reaction of CO gas-phase synthesis of oxalate
The characteristics of rate is high.
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 gas phase couplings synthesis grass
Acid esters catalyst, by weight percentage, including following component：1) 0.03~3wt% palladiums；2) 0.05~4wt% lanthanide series metals
Or its oxide；3) at least one of races of 0~3wt% the VIIIth metal or its oxide；4) 90~99.8wt% carriers, carrier choosing
At least one of self-alumina, silica or molecular sieve.
In above-mentioned technical proposal by weight percentage, preferred ingredient 3) content be 0.1~2wt%.
At least one of the VIIIth race metal or its oxide are preferably at least one of Fe, Co or Ni in above-mentioned technical proposal
Metal or its oxide.
At least one of the VIIIth race metal or its oxide are preferably at least one of Ru or Rh gold in above-mentioned technical proposal
Category or its oxide.
Lanthanide series metal or its oxide are preferably lanthanum or its oxide in above-mentioned technical proposal.
Preferably catalyst also includes being selected from for 0.005~1wt% to catalyst by weight percentage in above-mentioned technical proposal
At least one of the A races of the periodic table of elements V element or its oxide, element is selected from more preferably including 0.01~0.1wt%
At least one of the A races of periodic table V element or its oxide.
Element is preferably P or its oxide in the A races of the periodic table of elements V in above-mentioned technical proposal.
Element is preferably Sb or its oxide in the A races of the periodic table of elements V in above-mentioned technical proposal.
Element is preferably Bi or its oxide in the A races of the periodic table of elements V in above-mentioned technical proposal.
The preparation method of the CO gas phase coupling catalyst for synthesizing oxalic ester of the present invention, is mainly included the following steps that：
A) by water-soluble compound containing Pd, water-soluble lanthanun compound, water-soluble VIIIth compounds of group and water solubility
Vth A compounds of group is dissolved in water, is adjusted pH to 2~6 with hydrochloric acid and sodium carbonate, is obtained maceration extract I；
B) maceration extract I is impregnated or be sprayed at carrier, obtain catalyst precarsor；
C) catalyst precarsor is dried, roast, produces the oxalic acid ester catalyst.
Catalyst of the present invention is before use, can be handled as follows：In hydrogen or the gaseous mixture intermediate range of hydrogen and nitrogen
Sequence is warming up to 200 DEG C of reduction.
Due to the addition of group of the lanthanides, a variety of co-catalysis components of VIII race and V A races in the present invention so that the activearm on catalyst
Divide palladium that there is higher catalytic activity, the conversion ratio of methyl nitrite is higher in CO coupling synthesis of oxalate reactions, obtains more
High oxalate space-time yield, energy resource consumption and operating cost are advantageously reduced, while the investment of reactor can be substantially reduced, made
Existing synthesis of oxalate technique has more economy.Using the inventive method, nitrous acid ester conversion ratio can reach 89%, oxalic acid
Ester space-time yield can reach 1100g/L.H-1, achieve preferable technique effect.
In the inventive method, using following method of testing：
1) catalytic component is determined by ICP.
2) catalyst activity is evaluated：60g catalyst is taken to load in reaction tube, it is 500 small to be passed through hydrogen in volume space velocity
When-1, temperature programming to 200 DEG C reduce 6 hours.Then in 120 DEG C of reaction temperature, 0~0.5MPa of reaction pressure, raw material one aoxidizes
The mol ratio of carbon and nitrous acid ester is 1~2.5, and volume space velocity is 3000 hours-1Under the conditions of synthesizing dimethyl oxalate.
Below by specific embodiment, the invention will be further described.
Embodiment
【Embodiment 1】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.0.5g palladium bichlorides and 0.93g lanthanum nitrates is taken to be dissolved in
In 30ml water, it is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I 80 DEG C after carrier
Drying, 450 DEG C of roasts 4 hours, obtains catalyst cat-1A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 2】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichloride 0.93g lanthanum nitrates and 0.59g nitric acid
Nickel is dissolved in 30ml water, is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I in load
80 DEG C of drying after body, 450 DEG C of roasts 4 hours, obtain catalyst cat-2A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 3】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichloride 0.93g lanthanum nitrates and 7.4g nitric acid
Nickel is dissolved in 30ml water, is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I in load
80 DEG C of drying after body, 450 DEG C of roasts 4 hours, obtain catalyst cat-2A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 4】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichloride 0.93g lanthanum nitrates and 0.3g chlorinations
Rhodium is dissolved in 30ml water, is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I in load
80 DEG C of drying after body, 450 DEG C of roasts 4 hours, obtain catalyst cat-2A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 5】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichloride 0.93g lanthanum nitrates and 0.32g chlorine platinum
Acid is dissolved in 30ml water, is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I in load
80 DEG C of drying after body, 450 DEG C of roasts 4 hours, obtain catalyst cat-2A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 6】
Take 60g silica supports.0.5g palladium bichlorides, 0.93g lanthanum nitrates and 0.59g nickel nitrates is taken to be dissolved in 55ml water,
It is 3 with hydrochloric acid and sodium carbonate regulation pH, obtains maceration extract I, 80 DEG C of drying after carrier by the incipient impregnation of maceration extract I, 450 DEG C
Roast 4 hours, obtains catalyst cat-3A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 7】
Take 60g ZSM-5 carriers.Take 0.5g palladium bichlorides, 0.56g cerous nitrates and 0.3g nickel nitrates to be dissolved in 35ml water, use
Hydrochloric acid and sodium carbonate regulation pH are 3, obtain maceration extract I, 80 DEG C of drying after carrier by the incipient impregnation of maceration extract I, 450 DEG C of trainings
Burn 4 hours, obtain catalyst cat-4A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 8】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.03g palladium bichlorides, 0.09g neodymium nitrates and 0.3g vinegar
Sour cobalt is dissolved in 30ml water, with hydrochloric acid and sodium carbonate regulation pH be 3, obtain maceration extract I, by the incipient impregnation of maceration extract I in
80 DEG C of drying after carrier, 450 DEG C of roasts 4 hours, obtain catalyst cat-5A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 9】
Take 60g silica supports.Take 3.3g palladium bichlorides, 7.8g cerous nitrates and 8.5g ferric nitrates to be dissolved in 50ml water, use
Hydrochloric acid and sodium carbonate regulation pH are 3, obtain maceration extract I, 80 DEG C of drying after carrier by the incipient impregnation of maceration extract I, 450 DEG C of trainings
Burn 4 hours, obtain catalyst cat-6A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 10】
Take 60g silica supports.Take 1.05g palladium bichlorides, 2.8g cerous nitrates, 6.5g nickel nitrates and the dissolving of 0.85g zinc nitrates
In 50ml water, it is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I 80 after carrier
DEG C drying, 450 DEG C of roasts 4 hours, obtains catalyst cat-7A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 11】
Take 60g 4A type molecular sieve carriers.0.1g palladium bichlorides, 1.07g samaric nitrates and 0.16g ruthenium trichlorides is taken to be dissolved in
In 40ml water, it is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I 80 DEG C after carrier
Drying, 450 DEG C of roasts 4 hours, obtains catalyst cat-8A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 12】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 2.1g palladium bichlorides, 1.5g lanthanum nitrates and 2.7g acetic acid
Cobalt is dissolved in 30ml water, is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I in load
80 DEG C of drying after body, 450 DEG C of roasts 4 hours, obtain catalyst cat-9A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 13】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichlorides, 0.93g lanthanum nitrates, 0.59g nitric acid
Nickel and 0.01g phosphoric acid are dissolved in 30ml water, are 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I are obtained, by the grade body of maceration extract I
Product is impregnated in 80 DEG C of drying after carrier, 450 DEG C of roasts 4 hours, obtains catalyst cat-10A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 14】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichlorides, 0.93g lanthanum nitrates, 0.59g nitric acid
Nickel and 0.1g phosphoric acid are dissolved in 30ml water, are 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I are obtained, by the grade body of maceration extract I
Product is impregnated in 80 DEG C of drying after carrier, 450 DEG C of roasts 4 hours, obtains catalyst cat-11A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 15】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichlorides, 0.93g lanthanum nitrates, 0.59g nitric acid
Nickel and 1.2g antimony trichlorides are dissolved in 30ml water, are 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I are obtained, by maceration extract I
Incipient impregnation 80 DEG C of drying after carrier, 450 DEG C of roasts 4 hours, obtain catalyst cat-12A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 16】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichlorides, 0.93g lanthanum nitrates, 0.59g nitric acid
Nickel and 0.01g bismuth trichlorides are dissolved in 30ml water, are 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I are obtained, by maceration extract I
Incipient impregnation 80 DEG C of drying after carrier, 450 DEG C of roasts 4 hours, obtain catalyst cat-16A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Embodiment 17】
Take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichlorides, 0.93g lanthanum nitrates, 0.59g nitric acid
Nickel and 0.2g phosphoric acid are dissolved in 30ml water, are 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I are obtained, by the grade body of maceration extract I
Product is impregnated in 80 DEG C of drying after carrier, 450 DEG C of roasts 4 hours, obtains catalyst cat-17A.
【Embodiment 18】
Take 60g 4A type molecular sieve carriers.Take 0.1g palladium bichlorides, 1.07g samaric nitrates, 0.16g ruthenium trichlorides and 0.075g tri-
Bismuth chloride is dissolved in 40ml water, is 3 with hydrochloric acid and sodium carbonate regulation pH, maceration extract I is obtained, by the incipient impregnation of maceration extract I
80 DEG C of drying after carrier, 450 DEG C of roasts 4 hours, obtain catalyst cat-18A.
Catalytic component determines and Activity evaluation is shown in Table 1.
【Comparative example 1】
According to the preparation method of embodiment 1, palladium bichloride is simply only added in catalyst preparation process, is not added with lanthanide series metal
Compound, that is, take alumina supports of the 60g through 1200 DEG C of roastings 4 hours.Take 0.5g palladium bichlorides to be dissolved in 30ml water, use hydrochloric acid
It is 3 with sodium carbonate regulation pH, obtains maceration extract I, the incipient impregnation of maceration extract I is dried for 80 DEG C after carrier, 450 DEG C of roasts 4
Hour, obtain catalyst cat-1B.
Catalytic component determines and Activity evaluation is shown in Table 1.
Table 1
Claims (6)
1. one kind is used for CO gas phase coupling catalyst for synthesizing oxalic ester, by weight percentage, including following components：0.03 1)~
3wt% palladiums；2) 0.05~4wt% lanthanide series metals or its oxide；3) at least one of races of 0.1~2wt% the VIIIth metal or its
Oxide；At least one of VIIIth race metal or its oxide are Fe, Co, Ni, Ru or Rh；4) 90~99.8wt% is carried
Body, carrier are selected from least one of aluminum oxide, silica or molecular sieve；
The lanthanide series metal or its oxide are praseodymium, cerium, neodymium or samarium, or its oxide.
2. it is used for CO gas phase coupling catalyst for synthesizing oxalic ester according to claim 1, it is characterised in that with percentage by weight
Count catalyst and be selected from least one of the A races of the periodic table of elements V element or its oxide also including 0.005~1wt%.
3. it is used for CO gas phase coupling catalyst for synthesizing oxalic ester according to claim 2, it is characterised in that with percentage by weight
Count catalyst and be selected from least one of the A races of the periodic table of elements V element or its oxide also including 0.01~0.1wt%.
4. it is used for CO gas phase coupling catalyst for synthesizing oxalic ester according to claim 2, it is characterised in that selected from period of element
Element is P or its oxide in the A races of table V.
5. it is used for CO gas phase coupling catalyst for synthesizing oxalic ester according to claim 2, it is characterised in that selected from period of element
Element is Sb or its oxide in the A races of table V.
6. it is used for CO gas phase coupling catalyst for synthesizing oxalic ester according to claim 2, it is characterised in that selected from period of element
Element is Bi or its oxide in the A races of table V.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
| CN101850273A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Structured catalyst for synthesizing oxalate by CO gaseous-phase coupling and preparation method thereof |
| CN102649731A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing oxalate through CO gas phase coupling |
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| US20130150617A1 (en) * | 2010-06-04 | 2013-06-13 | Xinbin MA | Monolithic structured catalyst for carbon monoxide gase-phase coupling to dialkyl oxalate & preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596455A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | A kind of Catalysts and its preparation method of synthesis of oxalate |
| CN101850273A (en) * | 2010-06-04 | 2010-10-06 | 天津大学 | Structured catalyst for synthesizing oxalate by CO gaseous-phase coupling and preparation method thereof |
| CN102649731A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for producing oxalate through CO gas phase coupling |
Non-Patent Citations (2)
| Title |
|---|
| CO气相偶联制草酸酯研究进展;张旭;《工业催化》;20130831;第21卷(第8期);第12-17页 * |
| The mechanism of CO coupling reaction to form dimethyl oxalate over Pd/α-Al2O3;Yang Ji et al.;《Journal of Molecular Catalysis A: Chemical》;20090827;第314卷;第63-70页 * |
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