CN105582964B - A kind of O composite metallic oxide catalyst and its preparation method and application - Google Patents
A kind of O composite metallic oxide catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of O composite metallic oxide catalyst, it is to be doped with ZrO2Mo V (Te or Sb) Nb O class metal composite oxides, wherein the molar ratio of Zr elements and Mo elements is 0.00001~0.01:1.O composite metallic oxide catalyst of the present invention can improve the selectivity of oxidation of propane acrylic acid synthesizing to 85% or more under certain reaction condition, and yield is up to 45%.The present invention also provides the preparation methods of the catalyst and its application in oxidation of propane acrylic acid synthesizing.
Description
Technical field
The present invention relates to a kind of industrial catalysts, and in particular to a kind of O composite metallic oxide catalyst, more particularly to use
In the O composite metallic oxide catalyst of oxidation of propane acrylic acid synthesizing, and preparation method thereof.
Background technology
Propane is a kind of low-carbon saturated alkane, be natural gas, liquefied petroleum gas, coal bed gas, the main component of shale gas it
One, it is resourceful.Past is more as fuel, makees solvent on a small quantity, or for producing ethylene and propylene.Acrylicacidandesters class is
Series monomers are the monomers of most attractive synthetic polymer.Acrylic acid is mainly used for acrylic ester synthesizing and polypropylene
Acid, the latter is for producing hygienic material, detergent, dispersant, flocculant and thickener etc..Acrylate is then used to synthesize to apply
Material, adhesive, weaving, papermaking, leather and plastic additive etc..These polymer are in chemical stability, weatherability, durability, hard
Degree, flexibility, dissolubility and compatibility etc. show excellent performance.
The production technology of acrylic acid is propylene two-step oxidizing process at present has since propylene is the byproduct of petrochemical industry
Wide application field, therefore price is costly, and resource is extremely limited.If can be with resourceful, cheap
Propane replaces propylene that will bring considerable economic benefit as the raw material of production acrylic acid for manufacturing enterprise.
In the catalyst for selective oxidation of propane acrylic acid synthesizing studied at present, most of is that composition metal aoxidizes
Object, based on Mo, V, Te (Sb), Nb, the highest catalyst for Mitsubishi Corporation of Japan research and development of catalysis reaction yield, acrylic acid
Yield can reach 48%.Domestic Zhejiang University is by adulterating Cr into metal composite oxide, the acrylic acid on its catalyst
Yield is up to 50% or more.102056662 A of Chinese patent literature CN 102056661 A and CN then distinguishes doped metallic elements
W and Pd, to obtain high activity, however the selectivity of acrylic acid cannot still meet industrialized demand.
Invention content
It is an object of the invention to：Based on existing Research foundation, by adjusting adulterated in metal composite oxide at
Point provide a kind of new catalyst, it when this new catalyst is used for the technique of oxidation of propane acrylic acid synthesizing, can be substantially
Degree ground promotes the selectivity of acrylic acid.
Another object of the present invention is：The preparation method of the catalyst is provided.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of O composite metallic oxide catalyst is provided, it is to be doped with ZrO2The compound gold of Mo-V-Te (Sb)-Nb-O classes
Belong to oxide, wherein the molar ratio of Zr elements and Mo elements is 0.00001~0.01:1.
In currently preferred O composite metallic oxide catalyst, the metal composite oxide expression formula is：
Mo1VaTebNbcZrYOX, wherein a, b, c, Y, X are respectively the molar ratio of V, Te, Nb or Sb, Zr, O and Mo, and
Respective value is as follows：0.1≤a≤0.4,0.1≤b≤0.4,0.1≤c≤0.4,0.00001≤Y≤0.01,3.65≤X≤
6.2。
In the further preferred O composite metallic oxide catalyst of the present invention, the molar ratio of the Zr elements and Mo elements
It is 0.00002~0.002:1.
In the O composite metallic oxide catalyst of the present invention still further preferably, mole of the Zr elements and Mo elements
Than being 0.000023~0.00184:1.
In the most preferred O composite metallic oxide catalyst of the present invention, the Zr elements and the molar ratio of Mo elements are
0.000115~0.00138:1.
The present invention also provides the methods for preparing the O composite metallic oxide catalyst, include the following steps：
1) co-precipitation-infusion process is used, molybdate, metavanadate, telluric acid, niobium oxalate and ammonium salt solution are mixed, it is made
In Mo:V:Te:The molar ratio of Nb or Sb reaches 1:0.1~0.4:0.1~0.4:0.1~0.4, it then vacuumizes rotation and steams
It is dry, roast 2 hours for 200 DEG C in air atmosphere, then, then under an inert atmosphere 600 DEG C roast 2 hours, it is solid to obtain catalyst
Body；
2) catalyst solid obtained by step 1) is mixed with nitric acid aqueous zirconium, the molar ratio of Zr and Mo in solution is made to reach
0.00001~0.01:1, it after stirring 1~4 hour, is dried 3~6 hours at 120 DEG C, then 400~700 DEG C of roastings under an inert atmosphere
It burns 2~4 hours, obtains O composite metallic oxide catalyst of the present invention.
In preparation method of the present invention, the ammonium salt described in step 1) is preferably ammonium nitrate or ammonium sulfate.
The present invention also provides the O composite metallic oxide catalysts in the reaction of oxidation of propane acrylic acid synthesizing
Using the base stock of the reaction is propane, oxygen, nitrogen and water vapour, and reaction condition is that unstripped gas basic composition is：Third
Alkane:Oxygen:Nitrogen:The molar ratio of water vapour is 1:1.5~3:0~2:1.5~2, reaction temperature is 380~440 DEG C, and air speed is
1200~4500mL/g-cath.
Catalyst of the present invention is in Mo-V-Te (Sb)-Nb class O composite metallic oxide catalysts with specific
Ratio is doped with ZrO2, this O composite metallic oxide catalyst can be improved under certain reaction condition oxidation of propane synthesis third
For the selectivity of olefin(e) acid to 85% or more, yield reaches advanced level both domestic and external up to 45%.
Specific implementation mode
The present invention can be better understood according to embodiment below, however, these embodiments are only used for specifically
Bright technical scheme of the present invention, rather than limit the present invention.
Comparative example 1
At 80 DEG C in 350mL deionized waters 21.19 grams of ammonium molybdates of stirring and dissolving, 4.21 grams of ammonium metavanadates, 6.34 grams of telluriums
Acid and 1.30 grams of ammonium nitrate, stirring are down to room temperature after 2 hours, are slurry-A.
5.34 grams of niobium oxalates are dissolved in 200mL deionized waters at 80 DEG C, stirring is down to room temperature after 1 hour, is slurry-B.
Slurry-B is slowly added to slurry-A, is stirred 2 hours, it is dry to vacuumize rotary evaporated to dryness, is then dried at 120 DEG C
Overnight.
It is 5 millimeters of diameter, high about 2~3 millimeters of disk that solid after drying, which is granulated,.In air atmosphere, 200 DEG C of roastings
It burns 2 hours, then under an inert atmosphere, 600 DEG C roast 2 hours.As a result mixed-metal oxides are made
Mo1V0.3Te0.23Nb0.12Ox。
Embodiment 1
After the mixed-metal oxides of 20 grams of comparative example 1 are mixed with 400mL deionized waters, the nitre of 1g/L is added
Then sour aqueous zirconium 1mL is stirred 5 hours.Under vacuum-pumping conditions by obtained suspension, rotary evaporation is to being completely dried.
It is 5 millimeters of diameter, high about 2~3 millimeters of disk that solid after 120 DEG C of oven dried overnights, drying, which is granulated,.Then in inertia
Under atmosphere, 400 DEG C roast 2 hours.
Obtained solid particle is Zr:The molar ratio of Mo is 0.000023:1 by ZrO2The mixed-metal oxides of doping are urged
Agent.
Embodiment 2~9
Using the synthetic schemes of embodiment 1, only the dosage from embodiment 1 of zirconium nitrate solution is different, mole of Zr and Mo
Than as shown in table 1.The catalytic performance of catalyst is listed in Table 1 below.
The test condition of catalyst is as follows：
Under normal pressure, reaction temperature is 400 DEG C, air speed 1200mL/g-cath, propane:Oxygen:Water vapour=1:2:
2, loaded catalyst is 5 grams, and reactor is fixed-bed quartz reactor.
Product tail gas is analyzed by the online gas-chromatography equipped with 13X molecular sieves and Porapak Q packed columns, liquid
Product is then by ice-water bath condensed absorbent, and using normal propyl alcohol as internal standard, quantitative analysis is carried out by fid detector.
Table 1
| Embodiment is numbered | Zr:Mo (molar ratio) | Conversion of propane (%) | Acrylic acid selectivity (%) | Acrylic acid yield (%) |
| Embodiment 1 | 0.000023:1 | 45.37 | 60.28 | 27.35 |
| Embodiment 2 | 0.000115:1 | 50.44 | 62.20 | 31.37 |
| Embodiment 3 | 0.00023:1 | 58.22 | 68.54 | 38.82 |
| Embodiment 4 | 0.00046:1 | 66.73 | 75.22 | 42.00 |
| Embodiment 5 | 0.00092:1 | 70.03 | 85.28 | 45.19 |
| Embodiment 6 | 0.00138:1 | 62.73 | 77.32 | 39.50 |
| Embodiment 7 | 0.00184:1 | 55.33 | 69.18 | 35.64 |
| Comparative example 1 | 0 | 35.62 | 50.33 | 17.93 |
Claims (5)
1. a kind of O composite metallic oxide catalyst, it is characterised in that：It is to be doped with ZrO2Mo-V- (Te or Sb)-Nb-O classes
Metal composite oxide, metal composite oxide expression formula are：Mo1VaTebNbcZrYOX, wherein a, b, c, Y, X be respectively V,
The molar ratio of Te, Nb or Sb, Zr, O and Mo, and respectively value is as follows：0.1≤a≤0.4,0.1≤b≤0.4,0.1≤c≤
0.4,0.00023≤Y≤0.00046,3.65≤X≤6.2；
It is prepared by following methods：
1) co-precipitation-infusion process is used, molybdate, metavanadate, telluric acid, niobium oxalate and ammonium salt solution are mixed, made therein
Mo:V:Te:The molar ratio of Nb or Sb reaches 1:0.1~0.4:0.1~0.4:0.1~0.4, it then vacuumizes rotation and is evaporated,
Air atmosphere it is lower 200 DEG C roast 2 hours, then, then under an inert atmosphere 600 DEG C roast 2 hours, obtain catalyst solid；
2) catalyst solid obtained by step 1) is mixed with nitric acid aqueous zirconium, the molar ratio of Zr and Mo in solution is made to reach
0.00023~0.00046:1, after stirring 1~4 hour, dried 3~6 hours at 120 DEG C, then under an inert atmosphere 400~700
DEG C roasting 2~4 hours, obtains the O composite metallic oxide catalyst.
2. the method for preparing O composite metallic oxide catalyst described in claim 1, includes the following steps：
1) co-precipitation-infusion process is used, molybdate, metavanadate, telluric acid, niobium oxalate and ammonium salt solution are mixed, made therein
Mo:V:Te:The molar ratio of Nb or Sb reaches 1:0.1~0.4:0.1~0.4:0.1~0.4, it then vacuumizes rotation and is evaporated,
Air atmosphere it is lower 200 DEG C roast 2 hours, then, then under an inert atmosphere 600 DEG C roast 2 hours, obtain catalyst solid；
2) catalyst solid obtained by step 1) is mixed with nitric acid aqueous zirconium, the molar ratio of Zr and Mo in solution is made to reach
0.00023~0.00046:1, after stirring 1~4 hour, dried 3~6 hours at 120 DEG C, then under an inert atmosphere 400~700
DEG C roasting 2~4 hours, obtains the O composite metallic oxide catalyst.
3. preparation method according to claim 2, it is characterised in that：Ammonium salt described in step 1) is ammonium nitrate or sulfuric acid
Ammonium.
4. application of the O composite metallic oxide catalyst described in claim 1 in the reaction of oxidation of propane acrylic acid synthesizing.
5. application according to claim 4, it is characterised in that：The reaction of the oxidation of propane acrylic acid synthesizing it is basic
Raw material is propane, oxygen, nitrogen and water vapour, and reaction condition is that unstripped gas basic composition is：Propane:Oxygen:Nitrogen:Water vapour
Molar ratio be 1:1.5~3:0~2:1.5~2, reaction temperature is 380~440 DEG C, and air speed is 1200~4500mL/g-
cat·h。
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| CN111468136B (en) * | 2020-05-19 | 2021-06-15 | 西南化工研究设计院有限公司 | Catalyst for preparing acrylic acid by oxidizing propane and preparation method thereof |
| CN113083284B (en) * | 2021-04-13 | 2022-03-08 | 宁波昊祥新材料科技有限公司 | Mo-V-Te-Sb-Nb-O catalyst, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380933A (en) * | 1993-01-28 | 1995-01-10 | Mitsubishi Kasei Corporation | Method for producing an unsaturated carboxylic acid |
| EP0962253A2 (en) * | 1998-05-21 | 1999-12-08 | Rohm And Haas Company | A process for preparing a multi-metal oxide catalyst |
| CN101001696A (en) * | 2004-07-22 | 2007-07-18 | 马克斯·普朗克协会弗里茨·哈贝尔研究所 | Metal oxide catalyst and method for the preparation thereof |
| CN101722017A (en) * | 2008-10-22 | 2010-06-09 | 中国科学院大连化学物理研究所 | Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof |
| CN102395551A (en) * | 2009-04-16 | 2012-03-28 | 沙特基础工业公司 | A process for producing an unsaturated carboxylic acid from an alkane |
-
2014
- 2014-11-18 CN CN201410655737.7A patent/CN105582964B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5380933A (en) * | 1993-01-28 | 1995-01-10 | Mitsubishi Kasei Corporation | Method for producing an unsaturated carboxylic acid |
| EP0962253A2 (en) * | 1998-05-21 | 1999-12-08 | Rohm And Haas Company | A process for preparing a multi-metal oxide catalyst |
| CN101001696A (en) * | 2004-07-22 | 2007-07-18 | 马克斯·普朗克协会弗里茨·哈贝尔研究所 | Metal oxide catalyst and method for the preparation thereof |
| CN101722017A (en) * | 2008-10-22 | 2010-06-09 | 中国科学院大连化学物理研究所 | Molybdenum-vanadium-tellurium-niobium catalytic agent for preparing acrylic acid by propane oxidation and preparation method thereof |
| CN102395551A (en) * | 2009-04-16 | 2012-03-28 | 沙特基础工业公司 | A process for producing an unsaturated carboxylic acid from an alkane |
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Address after: 100029 Beijing Chaoyang District Shaoyaoju 101 North 1 1 18 Story 1 rooms 2101 rooms. Co-patentee after: DALIAN HETEROGENEOUS CATALYST CO., LTD. Patentee after: China catalyst Group Limited Address before: 100029 Beijing Chaoyang District Shaoyaoju 101 North 1 1 18 Story 1 rooms 2101 rooms. Co-patentee before: DALIAN HETEROGENEOUS CATALYST CO., LTD. Patentee before: CHINA CATALYST CO., LTD. |
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Effective date of registration: 20200522 Address after: 116023 Pine Island chemical industry park, Pu Wan new area, Liaoning, Dalian Patentee after: CHINA CATALYST NEW MATERIAL Co.,Ltd. Address before: 100029, Beijing, Shaoyaoju, Chaoyang District, North 101, 1, 18, 1, 2101 room Co-patentee before: CHINA CATALYST NEW MATERIAL Co.,Ltd. Patentee before: China catalyst Group Limited |
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