CN103894205A - Catalyst for acrylic acid synthesis and preparation method thereof - Google Patents
Catalyst for acrylic acid synthesis and preparation method thereof Download PDFInfo
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- CN103894205A CN103894205A CN201210576542.4A CN201210576542A CN103894205A CN 103894205 A CN103894205 A CN 103894205A CN 201210576542 A CN201210576542 A CN 201210576542A CN 103894205 A CN103894205 A CN 103894205A
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Abstract
The invention relates to a preparation method of a catalyst for acrylic acid synthesis, a catalyst prepared by the preparation method, and an acrylic acid synthesis method by using the catalyst, and aims to solve the problem of complex system brought by adoption of a two-section catalyst in the prior art. The catalyst is composed of the following components in percentage by weight: 40 to 60% of catalyst precursor I, 30% to 50% of catalyst precursor II, and 5% to 15% of adhesive, wherein the adhesive is SiO2 and/or Al2O3. The catalyst is prepared by mixing the catalyst precursor I, the catalyst precursor II, and the adhesive, and then subjecting the mixture to a forming process; wherein the catalyst precursor I is a catalyst for propylene oxidation for preparing acrolein, and the catalyst precursor II is a catalyst for acrolein oxidation for preparing acrylic acid. The catalyst well solves the problem mentioned above, and is capable of being applied to the industrial production of the catalyst for acrylic acid synthesis.
Description
Technical field
The present invention relates to the preparation method for the synthesis of acrylic acid catalyst and this catalyst.
Background technology
α is prepared in the selective oxidation of alkene, β unsaturated acids is important chemical process.Industrially conventionally first olefin oxidation is obtained to unsaturated aldehyde and then unsaturated aldehyde oxidation is obtained to unsaturated acids.Because this process adopts two sections of productions, use two reactors and two kinds of catalyst to complete under differential responses condition, therefore device is more numerous and diverse, and operation easier is large.One section of catalyst activity component is Mo, Bi composite oxides.The improvement of catalyst is mainly to carry out from the activity of catalyst 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; 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.
US Pat4224187,4248803 composition and their usage ratio and the method for preparing catalyst that propose by improving catalyst, improve olefin conversion and target product yield.For the selective oxidation of isobutene, there is the problem that reaction selectivity is low.Wherein isobutene conversion is up to 99%, but MAL, methacrylic acid total recovery only have 73.6%.
US Pat6268529 proposes a kind of propylene oxidation catalyst, propylene conversion 98.1%, methacrylaldehyde yield 65.3%, acrylic acid yield 20.8%, methacrylaldehyde, methacrylaldehyde total recovery 86.1%.
CN1564709 prepares and the catalyst non-uniform phenomenon that layering brings occurs between slaine in coprecipitation process improves catalyst performance by adding organic carboxyl acid to overcome catalyst.For the Selective Oxidation of propylene.Wherein propylene conversion is the highest by 98.12%, and methacrylaldehyde is selectively the highest by 82.53%, and methacrylaldehyde, acrylic acid total recovery are 91.05%.
Chinese patent ZL97191983.6, ZL00122609.6, ZL01111960.8 are reached and are controlled reaction focus, the object of extending catalyst stability by the catalyst layer axially increasing gradually to the multiple reactivities of outlet configuration from reaction gas inlet along reactor.Wherein the modulation of reactivity is by changing catalyst activity component and inert carrier ratio, changes in catalyst key component and realize as Bi, Fe and Mo ratio, catalyst calcination temperature and adjusting alkali metal kind consumption etc.
Two sections of catalyst use Mo, V catalyst conventionally, if US Pat7220698B2 is by adding a kind of catalyst poison of trace in catalyst preparation process, control catalyst reaction bed focus, suppress the thermal degradation of catalyst, improve 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 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%.The problem that prior art exists is mainly to use two-stage catalytic agent to bring the complexity of course of reaction, catalyst and device.Use a kind of catalyst for this reaction, due to the required Catalytic active phase difference of two-step reaction, the compositional optimization of catalyst is attended to one thing and lose sight of another unavoidably, cannot coordinate.
Summary of the invention
One of technical problem to be solved by this invention is the system complex problem that existing propylene oxidation acrylic acid catalyst processed uses two-stage catalytic agent to bring, a kind of preparation method for Selective Oxidation of Propylene acrylic acid catalyst processed is provided, and the catalyst that the method obtains can be by obtaining acrylic acid after a reactor.
Two of technical problem to be solved by this invention is the catalyst that obtain with above-mentioned preparation method.
Three of technical problem to be solved by this invention is the acrylic acid synthetic methods that adopt above-mentioned catalyst.
For one of solving the problems of the technologies described above, technical scheme of the present invention is as follows: a kind of preparation method for Selective Oxidation of Propylene acrylic acid catalyst processed, and described catalyst comprises the catalyst precarsor 1 of following component: 40-60% by weight percentage; The catalyst precarsor 2 of 30-50%; 5-15% binding agent, binding agent is SiO
2and/or Al
2o
3;
Wherein catalyst precarsor 1 is prepared methacrylaldehyde catalyst for propylene oxidation, to be selected from SiO
2or Al
2o
3in at least one be carrier, in molal quantity active constituent by following chemical formulation:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
qO
χ
Wherein X is at least one being selected from Mg, Co, Ca, Be, Cu, Zn, Pb or Mn; Y is at least one that select in Zr, Th or Ti; Z is at least one being selected from K, Rb, Na, Li, Tl or Cs; Q is at least one in La, Ce, Sm or Th; O is oxygen element; A, b, c, d, e, f, g and χ represent atomicity, and the span of a is 0.05～6.0; The span of b is 0.05～8.5; The span of c is 0.05～11.0; The span of d is 0.20～1.50; The span of e is 0.2～9.0; The span of f is 0.3～9.0; The span of g is >0～0.5; The span of q is 0.08～5.0; χ meets the required oxygen atom sum of other element valence; In catalyst precarsor 1, the consumption of carrier is 5～40% of catalyst precarsor 1 weight;
Wherein catalyst precarsor 2 is prepared by acrolein oxidation acrylic acid catalyst, to be selected from SiO
2, Al
2o
3or TiO
2in at least one be carrier, in molal quantity active constituent by following chemical formulation:
Mo
12V
a?Cu
b?X?
c?Y?
d?Z?
e?O
χ?
In formula, X is at least one being selected from W, Cr, Sn, Nb; Y is at least one being selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr, Sr; Z is at least one being selected from alkali metal or alkaline-earth metal; O is oxygen element; A b c d e and χ represent atomicity, and 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; χ meets the required oxygen atom sum of other element valence; In catalyst precarsor 2, the consumption of carrier is 5～40% of catalyst precarsor 2 weight;
The preparation process of described catalyst comprises:
(1) preparation of catalyst precarsor 1
I) ammonium molybdate of Kaolinite Preparation of Catalyst precursor 1 aequum and alkali metal salt are dissolved in water, then add the colloidal sol of catalyst precarsor 1 carrier aequum to form material 1;
II) Bi of Kaolinite Preparation of Catalyst precursor 1 aequum, Fe, Ni and the water soluble compound that is selected from X, Y, Z, Q are dissolved in and in water, form material 2;
III) under agitation, material 1 and material 2 are mixed to get to catalyst pulp 1;
IV) catalyst pulp 1 obtains catalyst precarsor 1 by spray shaping and preroast;
(2) preparation of precursor 2
I) ammonium metavanadate of aequum and ammonium molybdate are dissolved in water, then add the colloidal sol of catalyst precarsor 2 carrier aequums to form material 3;
Ii) Cu of Kaolinite Preparation of Catalyst precursor 2 aequums and the water soluble compound that is selected from X, Y, Z are dissolved in and in water, form material 4;
Iii) under agitation, material 3 and material 4 are mixed to get to catalyst pulp 2;
Iv) catalyst pulp 2 obtains catalyst precarsor 2 by spray shaping and preroast;
(3) described catalyst precarsor I and catalyst precarsor II are mixed with described binding agent, moulding obtains described catalyst.
In technique scheme, step IV) spray shaping condition is preferably: intake air temperature 320-350 ℃, air outlet temperature 115-135 ℃, atomizing disk rotating speed 12000-16000rpm; Step IV) pre-calcination temperature is preferably 450-550 ℃, preroast time and is preferably 60-120min; Step I v) spray shaping condition is preferably: intake air temperature 220-260 ℃, air outlet temperature 125-140 ℃, atomizing disk rotating speed 12000-16000rpm; Step I v) pre-calcination temperature is preferably 300-350 ℃, preroast time and is preferably 60-120min.
The mixing of step described in technique scheme (3) preferably adopts kneading, described moulding to adopt extrusion molding, and after extrusion molding, roasting obtains described catalyst; After the extrusion molding of step (3), the temperature of roasting is preferably 380-420 ℃; After the extrusion molding of step (3), the time of roasting is preferably 120min.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the catalyst that adopts the preparation method of catalyst described above to make.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: synthesis of conjugated carboxylic alkeneacid, under the existence of above-mentioned catalyst, reaction raw materials volume space velocity is 1000 ~ 1500 hours
-1, reaction temperature is 290 ~ 360 ℃, reaction pressure is 0 ~ 0.05MPa, represents that reaction raw materials consists of propylene: air: water vapour=1:8 ~ 10:0 ~ 3 with mol ratio.
Catalyst in the present invention is prepared acrylic acid, propylene for Selective Oxidation of Propylene: air: water vapour=1:9:1.5,330 ℃ of reaction temperatures, reaction pressure 0.02MPa, raw material volume space velocity 1300h
-1under condition, its propylene conversion is up to 98.2%, product acrylic acid yield is up to 88.2%, selectively up to 90.6%, and uses two-stage catalytic agent on year-on-year basis, and acrylic acid yield is significantly improved, and technological process is more succinct.
Below by embodiment, the present invention is further elaborated:
The specific embodiment
[embodiment 1]
1, catalyst preparation
(1) preparation of catalyst precarsor 1
By 1000 grams of (NH
4)
6mo
7o
244H
2o is dissolved in 1000 grams of water, adds the Ludox that 800 grams of concentration are 40 wt% to make material 1.
By 397 grams of Fe (NO
3)
39H
2o, 275 grams of Bi (NO
3)
35H
2o, 495 grams of Co (NO
3)
26H
2o, 452 grams of Ni (NO
3)
26H
2o, 42 grams of Mn (NO
3)
2, 20 grams of La (NO
3)
33H
2o, 2.9 grams of KNO
3and 5.5 grams of CsNO
3be dissolved in 212 grams of water and make material 2.
Material 2 is dripped under rapid stirring in material 1, form catalyst pulp 1, and at 80 ℃, stir after aging 2 hours slurry is carried out to spray shaping, the condition of spray shaping is: 340 ℃ of intake air temperatures, 125 ℃ of air outlet temperature; Atomizing disk rotating speed 14000rpm, obtains catalyst precarsor 1 through 500 ℃, 90min roasting after slurry spraying.The composition of catalyst precarsor 1 is listed in to table 1.
(2) preparation of catalyst precarsor 2
By 187 grams of NH
4vO
3and 1000 grams of (NH
4)
6mo
7o
244H
2o is dissolved in 3500 water, adds the aluminium colloidal sol that Ludox that 686 grams of concentration are 40wt% and 633 grams of concentration are 20wt% to make material 3.
By 166 grams of (NH
4)
6h
5[H
2(WO
4)
6], 328 grams of Ce (NO
3)
36H
2o, 263 grams of Zr (NO
3)
46H
2o, 319 grams of Cu (NO
3)
23H
2o and 92 grams of CsNO
3be dissolved in 200 grams of water, obtain material 4 after adding 33 grams of KOH to dissolve under then stirring.
Material 4 is dripped under rapid stirring in material 4, form catalyst pulp 2, and at 80 ℃, stir after aging 2 hours slurry is carried out to spray shaping, the condition of spray shaping is: 240 ℃ of intake air temperatures, 135 ℃ of air outlet temperature; Atomizing disk rotating speed 14000rpm, spray latter 320 ℃, 90min roasting of slurry obtain catalyst precarsor 2.The composition of catalyst precarsor 2 is listed in to table 2.
(3) get 1 and 400 grams of catalyst 2 of 600 grams of catalyst precarsors, adding 300 grams of concentration is the Ludox of 40 wt%, and the extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, and then 400 ℃, 90min roasting obtain catalyst.The main preparation condition of catalyst is listed in to table 3, the composition of catalyst is listed in to table 3.
2, evaluating catalyst
The investigation appreciation condition of catalyst is as follows:
Reactor: fixed bed single tube reactor, 25.4 millimeters of internal diameters, 3000 millimeters of reactor length
Catalyst: 800 grams
Reaction temperature: 330 ℃
Reaction pressure: 0.02MPa
Material molar ratio: propylene: air: water vapour=1:9:1.5
Raw material volume space velocity: 1300 hours
-1
Product absorbs with 0 ℃ of diluted acid, uses gas chromatographic analysis product.Propylene conversion, product yield and be optionally defined as:
The evaluating data of catalyst is listed in to table 7.
[embodiment 2-11]
1, catalyst preparation
(1) preparation of catalyst precarsor 1
Prepare material 1 and material 2 according to the step identical with embodiment 1, the composition of catalyst precarsor 1 is listed in table 1.Wherein preparing material 1 needed raw material is ammonium heptamolybdate, 40% Ludox and 20% aluminium colloidal sol; Preparing material 2 needed raw materials is that antimony oxide, all the other components are all used metal nitrate.
(2) preparation of catalyst precarsor 2
Prepare material 3 and material 4 according to the step identical with embodiment 1, the composition of catalyst precarsor 2 is listed in table 2.Wherein preparing material 1 needed raw material is ammonium heptamolybdate, ammonium metavanadate, 40% Ludox, 20% aluminium colloidal sol and titanium sulfate; Preparing material 2 needed raw materials is ammonium tungstate, antimony oxide, chromium trioxide, and all the other components are all used metal nitrate.(3) except adopting the catalyst precarsor 1 and catalyst precarsor 2 of corresponding embodiment separately, the consumption of catalyst precarsor 1 and catalyst precarsor 2, kind and the consumption of binding agent also change, and other preparation is all identical with embodiment 1 step (3).Shaping of catalyst condition is listed in table 3.
2, evaluating catalyst
Except adopting the catalyst of corresponding embodiment separately, other appreciation condition is all identical with embodiment 1 step 2.The evaluating data of catalyst is listed in to table 4.
[comparative example 1
]
1, catalyst preparation
The preparation of catalyst 1: according to embodiment 1 step (1) Kaolinite Preparation of Catalyst precursor 1, get 600 grams of catalyst precarsors 1 and add the Ludox that 180 grams of concentration are 40wt%, the extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, and then 400 ℃, 90min roasting obtain catalyst 1.
The preparation of catalyst 2: according to embodiment 1 step (2) Kaolinite Preparation of Catalyst precursor 2, get 400 grams of catalyst precarsors 1 and add the Ludox that 120 grams of concentration are 40wt%, the extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, and then 400 ℃, 90min roasting obtain catalyst 1.
3, evaluating catalyst
The trend of evaluating raw material is first flow through catalyst 1 and then the catalyst 2 of flowing through, and therefore the type of feed of catalyst is the first paragraph that 480 grams of catalyst 1 is seated in to reactor; 320 grams of catalyst 2 are seated in to second segment, and other appreciation condition is identical with embodiment 1, and the evaluating data of catalyst is listed in table 4.
[comparative example 2
]
During except evaluation, the type of feed of catalyst is different from comparative example 1, and the preparation of catalyst is all identical with comparative example 1 with evaluation.The type of feed of catalyst is to load after 1 and 320 grams of catalyst of 480 grams of catalyst 2 are evenly mixed.The evaluating data of catalyst is listed in to table 4.
[comparative example 3
]
1, catalyst preparation
(1) slurry 1 in embodiment 1 step (1) is mixed with the slurry 2 in embodiment 1 step (2), and at 80 ℃, stir after aging 2 hours slurry is carried out to spray shaping, the condition of spray shaping is identical with embodiment 1 step (2).
(2) get 1000 grams of the materials that step (1) obtains, adding 300 grams of concentration is the Ludox of 40 wt%, and the extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, and then 400 ℃, 90min roasting obtain catalyst.
2, evaluating catalyst
Except adopting the catalyst of comparative example 3, other appreciation condition is identical with embodiment 1.The evaluating data of catalyst is listed in to table 4.
the composition of table 1 catalyst precarsor 1
Note: χ meets the required oxygen atom sum of other element valence.
the composition of table 2 catalyst precarsor 2
Note: χ meets the required oxygen atom sum of other element valence.
table 3 shaping of catalyst condition
table 4, evaluating catalyst result
| Catalyst | Propylene conversion, % | Acrylic acid yield, % | Acrylic acid is selective, % |
| Embodiment 1 | 97.5 | 86.3 | 88.5 |
| Embodiment 2 | 96.9 | 87.5 | 90.3 |
| Embodiment 3 | 96.3 | 85.7 | 89.0 |
| Embodiment 4 | 97.5 | 87.3 | 89.5 |
| Embodiment 5 | 98.2 | 88.2 | 90.0 |
| Embodiment 6 | 97.9 | 85.2 | 87.0 |
| Embodiment 7 | 96.8 | 85.1 | 87.9 |
| Embodiment 8 | 98.0 | 85.6 | 87.3 |
| Embodiment 9 | 97.8 | 86.9 | 88.9 |
| Embodiment 10 | 96.2 | 87.2 | 90.6 |
| Embodiment 11 | 98.2 | 88.1 | 90.0 |
| Comparative example 1 | 95.6 | 81.2 | 84.9 |
| Comparative example 2 | 91.3 | 73.6 | 80.6 |
| Comparative example 3 | 87.4 | 66.8 | 76.4 |
Claims (10)
1. for a preparation method for Selective Oxidation of Propylene acrylic acid catalyst processed, described catalyst comprises the catalyst precarsor 1 of following component: 40-60% by weight percentage; The catalyst precarsor 2 of 30-50%; 5-15% binding agent, binding agent is SiO
2and/or Al
2o
3;
Wherein catalyst precarsor 1 is prepared methacrylaldehyde catalyst for propylene oxidation, to be selected from SiO
2or Al
2o
3in at least one be carrier, in molal quantity active constituent by following chemical formulation:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
qO
χ
Wherein X is at least one being selected from Mg, Co, Ca, Be, Cu, Zn, Pb or Mn; Y is at least one that select in Zr, Th or Ti; Z is at least one being selected from K, Rb, Na, Li, Tl or Cs; Q is at least one in La, Ce, Sm or Th; O is oxygen element; A, b, c, d, e, f, g and χ represent atomicity, and the span of a is 0.05～6.0; The span of b is 0.05～8.5; The span of c is 0.05～11.0; The span of d is 0.20～1.50; The span of e is 0.2～9.0; The span of f is 0.3～9.0; The span of g is >0～0.5; The span of q is 0.08～5.0; χ meets the required oxygen atom sum of other element valence; In catalyst precarsor 1, the consumption of carrier is 5～40% of catalyst precarsor 1 weight;
Wherein catalyst precarsor 2 is prepared by acrolein oxidation acrylic acid catalyst, to be selected from SiO
2, Al
2o
3or TiO
2in at least one be carrier, in molal quantity active constituent by following chemical formulation:
Mo
12V
a?Cu
b?X?
c?Y?
d?Z?
e?O
χ?
In formula, X is at least one being selected from W, Cr, Sn, Nb; Y is at least one being selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr, Sr; Z is at least one being selected from alkali metal or alkaline-earth metal; O is oxygen element; A b c d e and χ represent atomicity, and 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; χ meets the required oxygen atom sum of other element valence; In catalyst precarsor 2, the consumption of carrier is 5～40% of catalyst precarsor 2 weight;
The preparation process of described catalyst comprises:
(1) preparation of catalyst precarsor 1
I) ammonium molybdate of Kaolinite Preparation of Catalyst precursor 1 aequum and alkali metal salt are dissolved in water, then add the colloidal sol of catalyst precarsor 1 carrier aequum to form material 1;
II) Bi of Kaolinite Preparation of Catalyst precursor 1 aequum, Fe, Ni and the water soluble compound that is selected from X, Y, Z, Q are dissolved in and in water, form material 2;
III) under agitation, material 1 and material 2 are mixed to get to catalyst pulp 1;
IV) catalyst pulp 1 obtains catalyst precarsor 1 by spray shaping and preroast;
(2) preparation of precursor 2
I) ammonium metavanadate of aequum and ammonium molybdate are dissolved in water, then add the colloidal sol of catalyst precarsor 2 carrier aequums to form material 3;
Ii) Cu of Kaolinite Preparation of Catalyst precursor 2 aequums and the water soluble compound that is selected from X, Y, Z are dissolved in and in water, form material 4;
Iii) under agitation, material 3 and material 4 are mixed to get to catalyst pulp 2;
Iv) catalyst pulp 2 obtains catalyst precarsor 2 by spray shaping and preroast;
(3) described catalyst precarsor I and catalyst precarsor II are mixed with described binding agent, moulding obtains described catalyst.
2. according to the preparation method of the catalyst described in claims 1, it is characterized in that step IV) spray shaping condition is: intake air temperature 320-350 ℃, air outlet temperature 115-135 ℃, atomizing disk rotating speed 12000-16000rpm.
3. according to the preparation method of the catalyst described in claims 1, it is characterized in that step IV) pre-calcination temperature is that 450-550 ℃, preroast time are 60-120min.
4. according to the preparation method of the catalyst described in claims 1, it is characterized in that step I v) spray shaping condition be: intake air temperature 220-260 ℃, air outlet temperature 125-140 ℃, atomizing disk rotating speed 12000-16000rpm.
5. according to the preparation method of the catalyst described in claims 1, it is characterized in that step I v) pre-calcination temperature be that 300-350 ℃, preroast time are 60-120min.
6. according to the preparation method of the catalyst described in claims 1 to 5 any one, it is characterized in that the mixing of described step (3) adopts kneading, described moulding to adopt extrusion molding, after extrusion molding, roasting obtains described catalyst.
7. according to the preparation method of the catalyst described in claims 6, it is characterized in that the temperature of roasting is 380-420 ℃ after extrusion molding.
8. according to the preparation method of the catalyst described in claims 7, it is characterized in that after extrusion molding that the time of roasting is 120min.
9. the catalyst making according to the preparation method of the catalyst described in any one claim in claim 1 to 9.
10. synthesis of conjugated carboxylic alkeneacid, under the existence of catalyst as claimed in claim 1, reaction raw materials volume space velocity is 1000 ~ 1500 hours
-1, reaction temperature is 290 ~ 360 ℃, reaction pressure is 0 ~ 0.05MPa, represents that reaction raw materials consists of propylene: air: water vapour=1:8 ~ 10:0 ~ 3 with mol ratio.
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| CN103894205B (en) | 2016-02-10 |
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