CN103769148A - Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst - Google Patents

Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst Download PDF

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Publication number
CN103769148A
CN103769148A CN201210412575.5A CN201210412575A CN103769148A CN 103769148 A CN103769148 A CN 103769148A CN 201210412575 A CN201210412575 A CN 201210412575A CN 103769148 A CN103769148 A CN 103769148A
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China
Prior art keywords
catalyst
acrylic acid
span
acrolein oxidation
prepared
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CN201210412575.5A
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Inventor
缪晓春
杨斌
姚全明
汪国军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Priority to CN201210412575.5A priority Critical patent/CN103769148A/en
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Abstract

The invention relates to an acrolein oxidation to acrylic acid catalyst, a preparation method and an application of the catalyst, which mainly solve the problems of lower selectivity and yield of acrylic acid in the prior art. The problems are better solved by adopting the technical scheme that the catalyst takes at least one of SiO2, Al2O3 or TiO2 as a carrier and comprises an active component expressed by the following general formula: Mo12VaCuXcYdZeOx, wherein X is at least one of W, Cr, Sn or Nb, Y is at least one of Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr, and Z is at least one of alkali metal or alkaline-earth metal, and the catalyst can be used for industrial production of acrylic acid through acrolein oxidation.

Description

Acrolein oxidation is prepared acrylic acid catalyst, preparation method and its usage
Technical field
The present invention relates to a kind of acrolein oxidation and prepare acrylic acid catalyst, preparation method and its usage.
Background technology
It is important chemical process that α, β unsaturated aldehyde and unsaturated acids are prepared in the selective oxidation of alkene, the catalyst that wherein contains Mo, V by a kind of active component of the acrylic acid production and application of methacrylaldehyde system.The improvement of catalyst is mainly to carry out from the activity of catalyst, selective and stability aspect, as added transition metal to improve activity in active constituent, increases the single of product and receives; Add rare earth element to improve redox ability, improve catalyst stability; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, stabilizing catalyst activity component, improves the service life of catalyst etc.
Have a lot of patent reports for methacrylaldehyde selective oxidation:
US Pat7220698B2, by adding a kind of catalyst poison of trace in catalyst preparation process, controls catalyst reaction bed focus, suppresses the thermal degradation of catalyst, improves catalyst stability.Acrolein conversion rate reaches 98.8%, and keeps for a long time stable.US Pat7378367B2 has introduced a kind of acrylic acid catalyst, and acrylic acid yield is up to 95.1%, and has good stability, and in use procedure, reactor temperature rise is little.US Pat7456129B2 improves catalyst performance, acrolein conversion rate 98.9%, acrylic acid selective 95.1% by controlling carrier acid strength.
CN1183088C introduces a kind of method for preparing catalyst, and by selecting specific raw materials, acrolein conversion rate is up to 99.6%, and acrylic acid is selectively up to 96.0%, and acrylic acid yield is up to 95.2%.
In sum, in existing document, all there is the selective low and lower problem of acrylic acid yield of acrylic acid.
Summary of the invention
One of technical problem to be solved by this invention is the selective and lower problem of yield of acrylic acid in prior art, and a kind of new prepared by acrolein oxidation acrylic acid catalyst is provided.This catalyst is produced acrylic acid reaction for methacrylaldehyde selective oxidation, have advantages of acrylic acid selective high, acrylic acid yield is high.Two of technical problem to be solved by this invention is to provide the preparation method of the corresponding catalyst of a kind of catalyst used with technical solution problem.Three of technical problem to be solved by this invention is to provide a kind of purposes of described catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of acrolein oxidation is prepared acrylic acid catalyst, to be selected from SiO 2, Al 2o 3or TiO 2in at least one be carrier, active constituent is by following general formula:
Mo 12V aCu bX cY dZ eO x
In formula, X is at least one being selected from W, Cr, Sn or Nb;
Y is at least one being selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr;
Z is at least one being selected from alkali metal or alkaline-earth metal;
The span of a is 1.0～10.0;
The span of b is 0.5～8.0;
The span of c is 0.8～11.0;
The span of d is 0.5～6.0;
The span of e is 0.5～5.0;
X meets the required oxygen atom sum of other element valence;
In catalyst, the consumption of carrier is catalyst weight 5～40%;
In catalyst preparation process, add at least one the pore-creating compound that is selected from ammonium nitrate, ammonium carbonate, carbonic hydroammonium, starch, urea, polyvinyl alcohol or acetic acid.
In technique scheme, the value preferable range of a is 2.0～7.0; The value preferable range of b is 1.2～5.5; The value preferable range of c is 1.0～7.2; The value preferable range of d is 0.8～4.8; The value preferable range of e is 0.7～3.6.Y preferred version is at least one being selected from Fe, Bi, Ni, Sb, Ce, La, Zr or Sr.In catalyst, the consumption preferable range of carrier is catalyst weight 10～30%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method who is prepared acrylic acid catalyst by acrolein oxidation, comprises the following steps:
A) ammonium molybdate of aequum is dissolved in water, then by the SiO of aequum 2, Al 2o 3or TiO 2in at least one carrier add to obtain mixture
Figure 470081DEST_PATH_IMAGE001
;
B) by the ammonium metavanadate of aequum and be selected from ammonium nitrate, ammonium carbonate, carbonic hydroammonium, starch, urea, polyvinyl alcohol or acetic acid at least one be dissolved in and in water, form solution
Figure 84733DEST_PATH_IMAGE001
;
C) by the copper nitrate of aequum and be selected from slaine in W, Cr, Sn, Nb, Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr and be dissolved in and form solution in water
Figure 522668DEST_PATH_IMAGE002
;
D) under agitation, by solution
Figure 645082DEST_PATH_IMAGE001
and solution
Figure 852073DEST_PATH_IMAGE002
add respectively mixture
Figure 903205DEST_PATH_IMAGE001
form catalyst pulp;
E) slurry by spray shaping or evaporation most of moisture after extrusion molding obtain catalyst precursor, catalyst precursor obtains catalyst by 350-500 ℃ of roasting.
In technique scheme, in catalyst preparation process, the addition preferable range of pore-creating compound is to account for 2 ~ 10% of catalyst weight.Wherein, molybdenum source preferred version is from ammonium molybdate, and copper source preferred version is from copper nitrate or basic copper carbonate, and vanadium source preferred version is from ammonium metavanadate, and other are all from nitrate.
For solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: a kind of acrolein oxidation is prepared acrylic acid, wherein use catalyst be the catalyst one of technical solution problem Suo Shu.
In technique scheme, take methacrylaldehyde, air, water as raw material, its mol ratio is 1:(2.8 ~ 4): (1.5 ~ 3), preferable range is 1:(3 ~ 4): (1.8 ~ 3) are 1260 ~ 1540 hours in air speed -1, preferable range is 1300 ~ 1500 hours -1, pressure is 0.1 ~ 0.12MPa, and reaction temperature is under 260 ~ 290 ℃ of conditions, and raw material and catalyst haptoreaction generate acrylic acid.
The present invention is owing to having added pore-creating compound in catalyst preparation process, this pore-creating compound has increased the specific area of catalyst in Roasting Decomposition process, in catalyst, form special pore size distribution structure, make reactant be easy to absorption, product is easy to desorption, deep oxidation reaction is necessarily suppressed, thereby has improved the reactivity worth of catalyst.Using catalyst of the present invention to prepare methacrylaldehyde for Selective Oxidation of Propylene, is that 280 ℃, reaction velocity are 1400 hours in reaction temperature -1condition under, its acrolein conversion rate can reach 99.5%, acrylic acid selectively can reach 99.3%, product acrylic acid yield can reach 98.8%, improves nearly one percentage point than the yield of prior art, has obtained good technique effect.
In the embodiment providing below, to the investigation appreciation condition of catalyst be:
Reactor: fixed bed reactors, 25.4 millimeters of internal diameters, 750 millimeters of reactor length
Catalyst filling amount: 150 grams
Reaction temperature: 280 ℃
Reaction time: 4 hours
Raw material ratio: methacrylaldehyde/air/water steam=15.8/50.9/33.3
Reaction velocity: 1400 hours -1
Product absorbs with 0 ℃ of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance is valid data during at (95～105) %.
Acrolein conversion rate, product yield and be optionally defined as:
Figure 990427DEST_PATH_IMAGE004
Figure 255186DEST_PATH_IMAGE005
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[comparative example 1]
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds Ludox and 12.7 grams of (NH of 64.4 gram 40% (wt.) 4) 6h 5[H 2(WO 4) 6] make material A.
By 28.5 grams of Fe (NO 3) 39H 2o adds in 70 ℃ of hot water of 20 grams, adds 34.2 grams of Cu (NO after stirring and dissolving again 3) 23H 2o, 12.0 grams of Sr (NO 3) 2, make material B after 1.6 grams of KOH stirring and dissolving.
In 50 grams of water, add 25.8 grams of NH 4vO 3form material C.
Material B and C are successively dripped in material A under rapid stirring, form catalyst pulp, and at 80 ℃, stir aging 2 hours, extrusion molding after 120 ℃ of oven dry removal most of moisture of slurry, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 430 ℃, by above-mentioned examination condition, reaction appraisal result is listed in table 2.In comparative example 2, method for preparing catalyst, with comparative example 1, has just added urea in preparation process.
 
[embodiment 1]
By 100 grams of (NH 4) 6mo 7o 244H 2o joins in the warm water of 100 grams 70 ℃, stirs it is all dissolved, and adds aluminium colloidal sol and the 16.6 grams of (NH of the Ludox of 68.6 gram 40% (wt.), 63.3 gram 20% (wt.) 4) 6h 5[H 2(WO 4) 6] make material A.
By 32.8 grams of Ce (NO 3) 36H 2o adds in 70 ℃ of hot water of 20 grams, adds 26.3 grams of Zr (NO after stirring and dissolving again 3) 46H 2o, 31.9 grams of Cu (NO 3) 23H 2o, 64.1 grams, Bi (NO 3) 35H 2o, 9.2 grams of CsNO 3, 3.3 grams of KOH make material B after dissolving.
In 50 grams of water, add 18.7 grams of NH 4vO 3and 18 grams of urea form material C.
Material B and C are successively dripped in material A under rapid stirring, form catalyst pulp, and at 80 ℃, stir aging 2 hours, extrusion molding after 120 ℃ of oven dry removal most of moisture of slurry, obtain the cylinder of φ 3.5x3.5mm, then high-temperature roasting obtains catalyst finished product, and sintering temperature is 430 ℃.
 
[embodiment 2 ~ 11]
Make catalyst by each step of embodiment 1, just change catalyst preparation condition, add kind and the consumption of pore-creating compound, concrete outcome is listed in table 1, and under the identical appreciation condition of embodiment 1, reaction appraisal result is listed in table 2.
Table 1
Figure 975755DEST_PATH_IMAGE006
Table 2
? Acrylic acid yield (%) Acrylic acid selective (%) Acrolein conversion rate (%)
Comparative example 1 95.8 98.0 97.8
Comparative example 2 96.4 98.3 98.1
Embodiment 1 97.4 98.9 98.5
Embodiment 2 97.3 98.7 98.6
Embodiment 3 98.8 99.3 99.5
Embodiment 4 97.6 99.1 98.5
Embodiment 5 95.6 97.0 98.6
Embodiment 6 98.7 99.1 99.6
Embodiment 7 96.6 98.2 98.4
Embodiment 8 97.7 98.7 99.0
Embodiment 9 97.3 98.8 98.5
Embodiment 10 96.5 99.1 97.4
Embodiment 11 98.2 98.9 99.3

Claims (10)

1. acrolein oxidation is prepared an acrylic acid catalyst, to be selected from SiO 2, Al 2o 3or TiO 2in at least one be carrier, active constituent is by following general formula:
Mo 12V aCu bX cY dZ eO x
In formula, X is at least one being selected from W, Cr, Sn or Nb;
Y is at least one being selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr;
Z is at least one being selected from alkali metal or alkaline-earth metal;
The span of a is 1.0～10.0;
The span of b is 0.5～8.0;
The span of c is 0.8～11.0;
The span of d is 0.5～6.0;
The span of e is 0.5～5.0;
X meets the required oxygen atom sum of other element valence;
In catalyst, the consumption of carrier is catalyst weight 5～40%;
In catalyst preparation process, add at least one the pore-creating compound that is selected from ammonium nitrate, ammonium carbonate, carbonic hydroammonium, starch, urea, polyvinyl alcohol or acetic acid.
2. acrolein oxidation according to claim 1 is prepared acrylic acid catalyst, and the span that it is characterized in that a is 2.0～7.0; The span of b is 1.2～5.5; The span of c is 1.0～7.2; The span of d is 0.8～4.8; The span of e is 0.7～3.6.
3. acrolein oxidation according to claim 1 is prepared acrylic acid catalyst, it is characterized in that Y is at least one being selected from Fe, Bi, Ni, Sb, Ce, La, Zr or Sr.
4. acrolein oxidation according to claim 1 is prepared acrylic acid catalyst, and the consumption that it is characterized in that carrier in catalyst is catalyst weight 10～30%.
5. acrolein oxidation claimed in claim 1 is prepared the preparation method of acrylic acid catalyst, comprises the following steps:
A) ammonium molybdate of aequum is dissolved in water, then by the SiO of aequum 2, Al 2o 3or TiO 2in at least one carrier add to obtain mixture
Figure 162318DEST_PATH_IMAGE001
;
B) by the ammonium metavanadate of aequum and be selected from ammonium nitrate, ammonium carbonate, carbonic hydroammonium, starch, urea, polyvinyl alcohol or acetic acid at least one be dissolved in and in water, form solution
Figure 506711DEST_PATH_IMAGE001
;
C) by the copper nitrate of aequum and be selected from slaine in W, Cr, Sn, Nb, Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr and be dissolved in and form solution in water
Figure 440907DEST_PATH_IMAGE002
;
D) under agitation, by solution
Figure 946975DEST_PATH_IMAGE001
and solution add respectively mixture
Figure 858747DEST_PATH_IMAGE001
form catalyst pulp;
E) slurry by spray shaping or evaporation most of moisture after extrusion molding obtain catalyst precursor, catalyst precursor obtains catalyst by 350 ~ 500 ℃ of roastings.
6. acrolein oxidation according to claim 5 is prepared the preparation method of acrylic acid catalyst, it is characterized in that the addition of pore-creating compound in catalyst preparation process accounts for 2 ~ 10% of catalyst weight.
7. prepare the preparation method of acrylic acid catalyst according to the acrolein oxidation described in claims 5, it is characterized in that molybdenum source is from ammonium molybdate, copper source is from copper nitrate or basic copper carbonate, and vanadium source is from ammonium metavanadate, and other are all from nitrate.
8. acrolein oxidation is prepared an acrylic acid, it is characterized in that the catalyst using is catalyst claimed in claim 1.
9. according to claim 8ly prepare acrylic acid by acrolein oxidation, it is characterized in that, take methacrylaldehyde, air, water as raw material, its mol ratio is 1:(2.8 ~ 4): (1.5 ~ 3) are 1260 ~ 1540 hours in air speed -1, pressure is 0.1 ~ 0.12MPa, and reaction temperature is under 260 ~ 290 ℃ of conditions, and raw material and catalyst haptoreaction generate acrylic acid.
10. according to claim 9ly prepare acrylic acid by acrolein oxidation, the mol ratio that it is characterized in that methacrylaldehyde, air, water is 1:(3 ~ 4): (1.8 ~ 3), air speed is 1300 ~ 1500 hours -1.
CN201210412575.5A 2012-10-25 2012-10-25 Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst Pending CN103769148A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106423186A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN106423188A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN107282059A (en) * 2016-04-13 2017-10-24 中国石油化工股份有限公司 Produce the catalyst of acrylic acid
CN108421550A (en) * 2017-08-09 2018-08-21 上海华谊新材料有限公司 Catalyst and preparation method thereof for prepared by acrolein oxidation acrylic acid
CN110280257A (en) * 2019-07-10 2019-09-27 兰州科润化工技术有限公司 A kind of acrylic acid catalyst and preparation method thereof
CN110639536A (en) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation
CN110639506A (en) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 Catalyst for producing acrylic acid
CN111068711A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Acrylic acid catalyst and application thereof
CN111068675A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Supported catalyst for preparing acrylic acid from acrolein and application thereof
CN113649032A (en) * 2021-08-18 2021-11-16 金华永和氟化工有限公司 Vinylidene fluoride catalyst and preparation method thereof

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CN102371158A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Catalyst of acrylic acid prepared by oxidation process and its preparation method
CN102371163A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Unsaturated aldehyde catalyst prepared by oxidation method and preparation method thereof
CN103521235A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof

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CN102371158A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Catalyst of acrylic acid prepared by oxidation process and its preparation method
CN102371163A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Unsaturated aldehyde catalyst prepared by oxidation method and preparation method thereof
CN103521235A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106423188A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN106423188B (en) * 2015-08-12 2018-07-13 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method
CN106423186B (en) * 2015-08-12 2018-07-17 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN106423186A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN107282059A (en) * 2016-04-13 2017-10-24 中国石油化工股份有限公司 Produce the catalyst of acrylic acid
CN107282059B (en) * 2016-04-13 2020-08-07 中国石油化工股份有限公司 Catalyst for producing acrylic acid
CN108421550B (en) * 2017-08-09 2020-07-31 上海华谊新材料有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof
CN108421550A (en) * 2017-08-09 2018-08-21 上海华谊新材料有限公司 Catalyst and preparation method thereof for prepared by acrolein oxidation acrylic acid
CN110639536A (en) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation
CN110639506A (en) * 2018-06-27 2020-01-03 中国石油化工股份有限公司 Catalyst for producing acrylic acid
CN111068711A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Acrylic acid catalyst and application thereof
CN111068675A (en) * 2018-10-18 2020-04-28 中国石油化工股份有限公司 Supported catalyst for preparing acrylic acid from acrolein and application thereof
CN110280257A (en) * 2019-07-10 2019-09-27 兰州科润化工技术有限公司 A kind of acrylic acid catalyst and preparation method thereof
CN113649032A (en) * 2021-08-18 2021-11-16 金华永和氟化工有限公司 Vinylidene fluoride catalyst and preparation method thereof
CN113649032B (en) * 2021-08-18 2024-02-27 金华永和氟化工有限公司 Vinylidene fluoride catalyst and preparation method thereof

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