CN103894205B - Acrylic acid catalyst and preparation method thereof - Google Patents
Acrylic acid catalyst and preparation method thereof Download PDFInfo
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- CN103894205B CN103894205B CN201210576542.4A CN201210576542A CN103894205B CN 103894205 B CN103894205 B CN 103894205B CN 201210576542 A CN201210576542 A CN 201210576542A CN 103894205 B CN103894205 B CN 103894205B
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Abstract
The present invention relates to the catalyst that preparation method and the method for the synthesis of acrylic acid catalyst obtain and the synthesis of conjugated carboxylic alkeneacid adopting this catalyst, mainly solve the system complexity problems that the agent of prior art two-stage catalytic brings, by adopting: described catalyst comprises following component: the catalyst precarsor 1 of 40-60%; The catalyst precarsor 2 of 30-50%; 5-15% binding agent, binding agent is SiO
2and/or Al
2o
3; Described catalyst precarsor I and catalyst precarsor II is mixed with described binding agent, shaping, wherein catalyst precarsor 1 prepares methacrylaldehyde catalyst for propylene oxidation, wherein catalyst precarsor 2 is the technical scheme of prepared by acrolein oxidation acrylic acid catalyst, solve this technical problem preferably, can be used in the industrial production of synthesizing propylene acid catalyst.
Description
Technical field
The present invention relates to the preparation method for the synthesis of acrylic acid catalyst and this catalyst.
Background technology
It is important chemical process that α, β unsaturated acids is prepared in the selective oxidation of alkene.Industrially usually first olefin oxidation is obtained unsaturated aldehyde and then unsaturated aldehyde oxidation is obtained 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 carried out from the activity of catalyst and stability aspect, and as added transition metal to improve activity in active constituent, the list increasing product is received; Add rare earth element and improve redox ability; Add the elements such as Fe, Co, Ni to suppress the distillation of Mo, stabilizing catalyst activity component, improve the service life etc. of catalyst.
USPat4224187,4248803 proposes, by improving the composition of catalyst and their usage ratio and method for preparing catalyst, to 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%.
USPat6268529 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 overcomes in catalyst preparing coprecipitation process by adding organic carboxyl acid the catalyst non-uniform phenomenon that layering brings occurs between slaine improves catalyst performance.For the Selective Oxidation of propylene.Wherein propylene conversion is the highest by 98.12%, and acrolein selectivity is the highest by 82.53%, and methacrylaldehyde, acrylic acid total recovery are 91.05%.
Chinese patent ZL97191983.6, ZL00122609.6, ZL01111960.8 control reaction focus, the object of extending catalyst stability by axially reaching from reaction gas inlet to the catalyst layer that the multiple reactivity of outlet configuration increases gradually along reactor.Wherein the modulation of reactivity is by changing catalyst activity component and inert carrier ratio, changes in catalyst key component as Bi, Fe and Mo ratio, catalyst calcination temperature and regulate alkali metal kind consumption etc. to realize.
Two sections of catalyst use Mo, V catalyst usually, if USPat7220698B2 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 stable for a long time.USPat7378367B2 describes a kind of acrylic acid catalyst, and acrylic acid yield is up to 95.1%, and in use procedure, reactor temperature rise is little.USPat7456129B2 improves catalyst performance, acrolein conversion rate 98.9%, acrylic acid selectivity 95.1% by controlling support 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 selectivity is up to 96.0%, and acrylic acid yield is up to 95.2%.Prior art Problems existing mainly uses two-stage catalytic agent to bring the complexity of course of reaction, catalyst and device.Use a kind of catalyst for this reaction, needed for two-step reaction, Catalytic active phase is different, and 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 the agent of existing propylene oxidation acrylic acid catalyst use two-stage catalytic brings, there is provided a kind of preparation method for Selective Oxidation of Propylene acrylic acid catalyst, the catalyst that the method obtains can by obtaining acrylic acid after a reactor.
Two of technical problem to be solved by this invention is the catalyst obtained with above-mentioned preparation method.
Three of technical problem to be solved by this invention is the acrylic acid synthetic methods adopting 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, and described catalyst comprises following component: the catalyst precarsor 1 of 40-60%; The catalyst precarsor 2 of 30-50%; 5-15% binding agent, binding agent is SiO
2and/or Al
2o
3;
Wherein catalyst precarsor 1 prepares methacrylaldehyde catalyst, to be selected from SiO for propylene oxidation
2or Al
2o
3in at least one be carrier, with molar basis active constituent by following chemical formulation:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
qO
χ
Wherein X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb or Mn; Y is at least one selected in Zr, Th or Ti; Z is at least one be 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 is for meeting the oxygen atom sum needed for 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, with molar basis 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 be selected from W, Cr, Sn, Nb; Y is at least one be selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr, Sr; Z is selected from least one in alkali metal or alkaline-earth metal; O is oxygen element; A b c d e and χ represents 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 is for meeting the oxygen atom sum needed for 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, and the colloidal sol then adding catalyst precarsor 1 carrier aequum forms material 1;
II) Bi, Fe, Ni of Kaolinite Preparation of Catalyst precursor 1 aequum and the water soluble compound that is selected from X, Y, Z, Q are dissolved in water form material 2;
III) under agitation, material 1 and material 2 are mixed to get catalyst pulp 1;
IV) catalyst pulp 1 obtains catalyst precarsor 1 by spray shaping and preroast;
(2) preparation of precursor 2
I) be dissolved in water by the ammonium metavanadate of aequum and ammonium molybdate, the colloidal sol then adding catalyst precarsor 2 carrier aequum forms material 3;
Ii) Cu of Kaolinite Preparation of Catalyst precursor 2 aequum and the water soluble compound that is selected from X, Y, Z are dissolved in water form material 4;
Iii) under agitation, material 3 and material 4 are mixed to get 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 mixed with described binding agent, shapingly obtain described catalyst.
In technique scheme, step IV) spray shaping condition is preferably: intake air temperature 320-350 DEG C, air outlet temperature 115-135 DEG C, atomizing disk rotating speed 12000-16000rpm; Step IV) pre-calcination temperature is preferably 450-550 DEG C, pre-firing times is preferably 60-120min; Step I v) spray shaping condition is preferably: intake air temperature 220-260 DEG C, air outlet temperature 125-140 DEG C, atomizing disk rotating speed 12000-16000rpm; V) pre-calcination temperature is preferably 300-350 DEG C to step I, pre-firing times is preferably 60-120min.
The mixing of step described in technique scheme (3) preferably adopts kneading, described shaping employing 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 DEG C; After the extrusion molding of step (3), the time of roasting is preferably 120min.
In order to solve the problems of the technologies described above two, technical scheme of the present invention is as follows: adopt the catalyst that the preparation method of catalyst described above obtains.
In order to solve the problems of the technologies described above three, technical scheme of the present invention is as follows: synthesis of conjugated carboxylic alkeneacid, and under the existence of above-mentioned catalyst, reaction raw materials volume space velocity is 1000 ~ 1500 hours
-1, reaction temperature is 290 ~ 360 DEG C, and reaction pressure is 0 ~ 0.05MPa, represents that reaction raw materials consists of propylene: air with mol ratio: water vapour=1:8 ~ 10:0 ~ 3.
Catalyst in the present invention is used for Selective Oxidation of Propylene and prepares acrylic acid, propylene: air: water vapour=1:9:1.5, reaction temperature 330 DEG C, reaction pressure 0.02MPa, raw material volume air speed 1300h
-1under condition, its propylene conversion is up to 98.2%, product propylene acid yield is up to 88.2%, selective up to 90.6%, with the agent of use two-stage catalytic on year-on-year basis, acrylic acid yield is significantly improved, and technological process is more succinct.
Below by embodiment, the present invention is further elaborated:
Detailed description of the invention
[embodiment 1]
1, catalyst preparing
(1) preparation of catalyst precarsor 1
By 1000 grams of (NH
4)
6mo
7o
244H
2o is dissolved in 1000 grams of water, and adding 800 grams of concentration is that material 1 made by the Ludox of 40wt%.
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.
Dripped under fast stirring by material 2 in material 1, form catalyst pulp 1, and carry out spray shaping to slurry stir aging 2 hours at 80 DEG C after, the condition of spray shaping is: intake air temperature 340 DEG C, air outlet temperature 125 DEG C; Atomizing disk rotating speed 14000rpm, after slurry spraying through 500 DEG C, 90min roasting obtains catalyst precarsor 1.The composition of catalyst precarsor 1 is listed in 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, and adding Ludox that 686 grams of concentration are 40wt% and 633 grams of concentration is that the Alumina gel of 20wt% makes 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 gram CsNO
3be dissolved in 200 grams of water, add under then stirring after 33 grams of KOH dissolve and obtain material 4.
Dripped under fast stirring by material 4 in material 4, form catalyst pulp 2, and carry out spray shaping to slurry stir aging 2 hours at 80 DEG C after, the condition of spray shaping is: intake air temperature 240 DEG C, air outlet temperature 135 DEG C; Atomizing disk rotating speed 14000rpm, latter 320 DEG C of slurry spraying, 90min roasting obtain catalyst precarsor 2.The composition of catalyst precarsor 2 is listed in table 2.
(3) get 600 grams of catalyst precarsors 1 and 400 grams of catalyst 2, adding 300 grams of concentration is the Ludox of 40wt%, and extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, then 400 DEG C, 90min roasting obtains catalyst.The main preparation condition of catalyst is listed in table 3, the composition of catalyst is listed in table 3.
, evaluating catalyst
The investigation appreciation condition of catalyst is as follows:
Reactor: fixed bed single tube reactor, internal diameter 25.4 millimeters, reactor length 3000 millimeters
Catalyst: 800 grams
Reaction temperature: 330 DEG C
Reaction pressure: 0.02MPa
Material molar ratio: propylene: air: water vapour=1:9:1.5
Raw material volume air speed: 1300 hours
-1
Product 0 DEG C of diluted acid absorbs, and uses gas chromatographic analysis product.Propylene conversion, product yield and be optionally defined as:
The evaluating data of catalyst is listed in table 7.
[embodiment 2-11]
1, catalyst preparing
(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 lists in table 1.Wherein preparing material 1 needed raw material is ammonium heptamolybdate, 40% Ludox and 20% Alumina gel; Prepare that material 2 needed raw material is antimony oxide, all the other components all use 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 lists in table 2.Wherein preparing material 1 needed raw material is ammonium heptamolybdate, ammonium metavanadate, 40% Ludox, 20% Alumina gel and titanium sulfate; Preparing material 2 needed raw material is ammonium tungstate, antimony oxide, chromium trioxide, and all the other components all use metal nitrate.(3) except the catalyst precarsor 1 that adopts corresponding embodiment separately and catalyst precarsor 2, the consumption of catalyst precarsor 1 and catalyst precarsor 2, the kind of binding agent and consumption also change, and other preparation is all identical with embodiment 1 step (3).Shaping of catalyst condition lists in table 3.
, 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 table 4.
[comparative example 1
]
1, catalyst preparing
The preparation of catalyst 1: according to embodiment 1 step (1) Kaolinite Preparation of Catalyst precursor 1, getting 600 grams of catalyst precarsors 1, to add 180 grams of concentration be the Ludox of 40wt%, extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, then 400 DEG C, 90min roasting obtains catalyst 1.
The preparation of catalyst 2: according to embodiment 1 step (2) Kaolinite Preparation of Catalyst precursor 2, getting 400 grams of catalyst precarsors 1, to add 120 grams of concentration be the Ludox of 40wt%, extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, then 400 DEG C, 90min roasting obtains catalyst 1.
, evaluating catalyst
The trend evaluating raw material first flows through catalyst 1 and then flows through catalyst 2, and therefore the type of feed of catalyst is the first paragraph 480 grams of catalyst 1 being seated in reactor; 320 grams of catalyst 2 are seated in second segment, and other appreciation condition is identical with embodiment 1, and the evaluating data of catalyst lists in table 4.
[comparative example 2
]
Except when evaluating, the type of feed of catalyst is different from except comparative example 1, the preparation of catalyst is all identical with comparative example 1 with evaluation.The type of feed of catalyst is, loads after 480 grams of catalyst 1 and 320 grams of catalyst 2 Homogeneous phase mixing.The evaluating data of catalyst is listed in table 4.
[comparative example 3
]
1, catalyst preparing
(1) mixed with the slurry 2 in embodiment 1 step (2) by the slurry 1 in embodiment 1 step (1), and carry out spray shaping to slurry stir aging 2 hours at 80 DEG C after, the condition of spray shaping is identical with embodiment 1 step (2).
(2) get the material 1000 grams that step (1) obtains, adding 300 grams of concentration is the Ludox of 40wt%, and extrusion molding of kneading obtains the Raschig ring of φ 3.5x3.5mm, then 400 DEG C, 90min roasting obtains catalyst.
, 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 table 4.
the composition of table 1 catalyst precarsor 1
Note: χ is for meeting the oxygen atom sum needed for other element valence.
the composition of table 2 catalyst precarsor 2
Note: χ is for meeting the oxygen atom sum needed for other element valence.
table 3 shaping of catalyst condition
table 4, evaluating catalyst result
| Catalyst | Propylene conversion, % | Acrylic acid yield, % | Acrylic acid selectivity, % |
| 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, described catalyst comprises following component: the catalyst precarsor 1 of 40-60%; The catalyst precarsor 2 of 30-50%; 5-15% binding agent, binding agent is SiO
2and/or Al
2o
3;
Wherein catalyst precarsor 1 prepares methacrylaldehyde catalyst, to be selected from SiO for propylene oxidation
2or Al
2o
3in at least one be carrier, with molar basis active constituent by following chemical formulation:
Mo
12Bi
aFe
bNi
cSb
dX
eY
fZ
gQ
qO
χ
Wherein X is at least one be selected from Mg, Co, Ca, Be, Cu, Zn, Pb or Mn; Y is at least one selected in Zr, Th or Ti; Z is at least one be 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 and non-vanishing; The span of q is 0.08 ~ 5.0; χ is for meeting the oxygen atom sum needed for 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, with molar basis active constituent by following chemical formulation:
Mo
12V
a′Cu
b′X′
c′Y′
d′Z′
e′O
χ′
In formula, X ' is for being selected from least one in W, Cr, Sn, Nb; Y ' is for being selected from least one in Fe, Bi, Co, Ni, Sb, Ce, La, Zr, Sr; Z ' is for being selected from least one in alkali metal or alkaline-earth metal; O is oxygen element; A ' b ' c ' d ' e ' and χ ' expression atomicity, 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 ' is for meeting the oxygen atom sum needed for 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, and the colloidal sol then adding catalyst precarsor 1 carrier aequum forms material 1;
II) Bi, Fe, Ni of Kaolinite Preparation of Catalyst precursor 1 aequum and the water soluble compound that is selected from X, Y, Z, Q are dissolved in water form material 2;
III) under agitation, material 1 and material 2 are mixed to get catalyst pulp 1;
IV) catalyst pulp 1 obtains catalyst precarsor 1 by spray shaping and preroast;
(2) preparation of precursor 2
I) be dissolved in water by the ammonium metavanadate of aequum and ammonium molybdate, the colloidal sol then adding catalyst precarsor 2 carrier aequum forms material 3;
Ii) by the Cu of Kaolinite Preparation of Catalyst precursor 2 aequum and be selected from X ', Y ', the water soluble compound of Z ' is dissolved in water and forms material 4;
Iii) under agitation, material 3 and material 4 are mixed to get 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 mixed with described binding agent, shapingly obtain described catalyst.
2. the preparation method of catalyst according to claim 1, is characterized in that step IV) spray shaping condition is: intake air temperature 320-350 DEG C, air outlet temperature 115-135 DEG C, atomizing disk rotating speed 12000-16000rpm.
3. the preparation method of catalyst according to claim 1, is characterized in that step IV) pre-calcination temperature is 450-550 DEG C, pre-firing times is 60-120min.
4. the preparation method of catalyst according to claim 1, is characterized in that step I v) spray shaping condition is: intake air temperature 220-260 DEG C, air outlet temperature 125-140 DEG C, atomizing disk rotating speed 12000-16000rpm.
5. the preparation method of catalyst according to claim 1, is characterized in that step I v) pre-calcination temperature is 300-350 DEG C, pre-firing times is 60-120min.
6. the preparation method of the catalyst according to any one of claim 1 to 5, it is characterized in that the mixing of described step (3) adopts kneading, described shaping employing extrusion molding, after extrusion molding, roasting obtains described catalyst.
7. the preparation method of catalyst according to claim 6, after it is characterized in that extrusion molding, the temperature of roasting is 380-420 DEG C.
8. the preparation method of catalyst according to claim 7, after it is characterized in that extrusion molding, the time of roasting is 120min.
9. according to the catalyst that the preparation method of the catalyst any one of claim 1 to 8 described in claim obtains.
10. synthesis of conjugated carboxylic alkeneacid, under the existence of the catalyst obtained in preparation method as claimed in claim 1, reaction raw materials volume space velocity is 1000 ~ 1500 hours
-1, reaction temperature is 290 ~ 360 DEG C, and reaction pressure is 0 ~ 0.05MPa, represents that reaction raw materials consists of propylene: air with mol ratio: water vapour=1:8 ~ 10:0 ~ 3.
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| WO2020203606A1 (en) * | 2019-03-29 | 2020-10-08 | 日本化薬株式会社 | Dried granules for catalyst production, catalyst, and compound production method |
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