CN107282057A - For synthesis of acrolein and the catalyst of acrylic acid - Google Patents
For synthesis of acrolein and the catalyst of acrylic acid Download PDFInfo
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- CN107282057A CN107282057A CN201610227758.8A CN201610227758A CN107282057A CN 107282057 A CN107282057 A CN 107282057A CN 201610227758 A CN201610227758 A CN 201610227758A CN 107282057 A CN107282057 A CN 107282057A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
- C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to the catalyst for synthesis of acrolein and acrylic acid.Technical scheme is as follows：For synthesis of acrolein and the catalyst of acrylic acid, including following components in terms of parts by weight：Macropore Si Al oxide carriers, 35 80 parts；Active component thereon, 20 65 parts are loaded in it；The active component is expressed as Mo with atomicity12BiaNicQsYeZfOx；Wherein Q is selected from least one of Mg, Co, Ca, Be, Cu, Zn, Pb, Mn, Fe；Y is selected from least one of K, Rb, Na, Li or Cs；Z is at least one of La, Ce or Sm；A is Bi atomicities；C is Ni atomicities；S is Q atomicities；E is Y atomicities；F is Z atomicities；X is the oxygen atom sum needed for meeting other element valences.
Description
Technical field
The present invention relates to the catalyst for synthesis of acrolein and acrylic acid, the preparation method of the catalyst, the catalysis
Application of the agent in synthesis of acrolein and acrylic acid, and methacrylaldehyde and synthesis of conjugated carboxylic alkeneacid.
Background technology
Acrylic acid (CH2=CH-COOH) it is simplest unsaturated carboxylic acid, it is important organic synthesis raw material and synthesis
Resin monomer.Acrylic acid is mainly used in synthesizing senior water-absorbing resins and water treatment agent etc., and a part of acrylic acid is used to be esterified
To manufacture the esters of acrylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-EHA,
And acrylate polymer is mainly used in the fields such as adhesive, coating, weaving, plastics, leather, papermaking.
In recent years acrylic acid and its series of products are developed rapidly, 2013, acrylicacidandesters class whole world total output
607.6 ten thousand t/a are reached, 515.6 ten thousand t/a compared with the end of the year in 2010 increase 17.8%, the production dress of current acrylic acid
Put and be concentrated mainly on the U.S., Europe, Japan and China, wherein China is acrylic acid production capacity country with fastest developing speed in recent years,
China in 2012 is simultaneously more than US and European, as the country that acroleic acid device production capacity in the world is maximum.Whole world industry
The large-scale plant for producing acrylic acid all uses propylene oxidation technology, and the technology has had the history of decades, substantial amounts of technology
Exploitation makes its production technology be gradually improved.
The shaping of catalyst preparation process of prior art, be typically all first be made into slurry, then spray, mediate, extrusion into
Type, finally it is calcined.But inventors herein have recognized that, in the reaction that propylene oxidation prepares methacrylaldehyde and acrylic acid,
With substantial amounts of heat release, generation focus, and work on the preformed catalyst that can touch of reaction substrate propylene are very easy to
Property component complexity just determine the final reaction effect of catalyst, therefore it is rationally scattered to prepare active component
Catalyst is the difficult point of this area catalyst technology.
Chinese patent CN1564709 can overcome co-precipitation to prepare catalysis to a certain extent by adding organic carboxyl acid
It is layered between metal salt produced by during agent so that in precipitation process, each Metal Distribution is more uniform,
So as to improve catalyst performance.
Catalyst of the Chinese patent CN1089081C using Mo, Bi and Fe as basic element, by adjusting Element Species
Class and content, and by further adjusting the type of feed of catalyst in the reactor, it is to avoid the generation of focus in reaction,
And it is avoided that peroxidization.But the problem of there is methacrylaldehyde plus low acrylic acid total recovery in existing catalyst.
But in propylene oxidation prepares methacrylaldehyde and propylene acid reaction, with substantial amounts of heat release, and reaction substrate propylene
The complexity of active component just determines the final reaction effect of catalyst, therefore system on the preformed catalyst that can be touched
For active component high degree of dispersion, and the catalyst with a large amount of macroporous structures is gone out, propylene oxidation reaction effect is carried
Rise and beds radiating tool has obvious benefits.
The content of the invention
One of technical problems to be solved by the invention are existing anti-in propylene oxidation production methacrylaldehyde and acrylic acid in the art
There is provided a kind of catalyst for the problem of catalyst activity and selectivity present in answering is relatively low.The catalyst is aoxidized for propylene
Methacrylaldehyde and propylene acid reaction are produced, with methacrylaldehyde and sour high income, the characteristics of stability is good.
The two of the technical problems to be solved by the invention are to provide the preparation method of one of above-mentioned technical problem catalyst.
The three of the technical problems to be solved by the invention are to provide one of above-mentioned technical problem catalyst and aoxidized in propylene
Produce the application in methacrylaldehyde and acrylic acid.
The four of the technical problems to be solved by the invention are to provide the propylene using one of the above-mentioned technical problem catalyst
The synthetic method of aldehyde and acid.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：
For synthesis of acrolein and the catalyst of acrylic acid, including following components in terms of parts by weight：
Macropore Si-Al oxide carriers, 35-80 parts；
Active component thereon, 20-65 parts are loaded in it；
The active component is expressed as Mo with atomicity12BiaNicQsYeZfOx；
Wherein Q is selected from least one of Mg, Co, Ca, Be, Cu, Zn, Pb, Mn, Fe；Y be selected from
At least one of K, Rb, Na, Li or Cs；Z is at least one of La, Ce or Sm；A is Bi atomicities；
C is Ni atomicities；S is Q atomicities；E is Y atomicities；F is Z atomicities；X is to meet other element compounds
Oxygen atom sum needed for valency.
In above-mentioned technical proposal, a span is preferably 0.05~6.0.
In above-mentioned technical proposal, c span is preferably 0.05~6.0.
In above-mentioned technical proposal, s span is preferably 0.05~6.0.
In above-mentioned technical proposal, e span is preferably 0~0.5.
In above-mentioned technical proposal, f span is preferably 0~5.0.
As preferred technical scheme, Q simultaneously including Fe and X, X be selected from Mg, Co, Ca, Be, Cu, Zn,
Pb, Mn are at least one, namely activity expression formula is：Mo12BiaFebNicXdYeZfOx,
In above-mentioned technical proposal, b span is preferably 0.05~4.0.
In above-mentioned technical proposal, d span is preferably 0.2~6.0.
In above-mentioned technical proposal, the average pore size of described macropore Si-Al oxide carriers is preferably 0.5-2.5 microns.
In above-mentioned technical proposal, the Si/Al mol ratios of the macropore Si-Al oxide carriers are not particularly limited.For example but
It is not limited to 0.5~3.
As technical scheme even more preferably, the catalyst use include first with the carrier with Fe and according to
Mo:Fe mol ratio loads Fe and Mo for the Mo mixed impregnant liquors needed for 0.1~4, and then roasting is further born
When carrying rest activity element and being prepared the step of roasting, the conversion ratio and aldehyde of propylene and sour total recovery are higher than other loads
Sequentially.The Mo:Fe mol ratio most preferably 0.5~4, the most preferably 0.5~2.
The key point of catalyst of the present invention does not lie in the geometry and size of catalyst, therefore to the shape and chi of catalyst
Very little to be not particularly limited, the variously-shaped and size of existing carrier is used equally for the present invention and obtains year-on-year result.For example
The carrier of the present invention can take spherical, Raschig ring or cylinder etc..Preferable 3~the 5mm of spherical diameter；Outside Raschig ring
Preferable 4~the 7mm in footpath, internal diameter preferably 1.5~3mm, length preferably 3~5mm；Preferable 4~the 7mm of cylindrical outer diameter,
Length preferably 3~5mm.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One of above-mentioned technical problem skill
The preparation method of catalyst, comprises the following steps any one of art scheme：
(a), by all required Fe compound and according to Mo:Chemical combination of the Fe mol ratio for the Mo needed for 0.5~2
Thing is soluble in water to obtain Fe, Mo mixed solution, and the pH value that solution is adjusted with ammoniacal liquor is 3-6, obtains aqueous solution I.
(b), macropore Si-Al oxide carriers are mixed with aqueous solution I, are dried, and roasting obtains catalyst precarsor α.
(c), the desired amount of Bi, Ni, X, Y, Z and the Mo of surplus soluble-salt are dissolved in the water, obtained
Aqueous dispersion II.
(d), catalyst precarsor α is mixed with aqueous dispersion II, is dried, and roasting obtains described catalyst.
In above-mentioned technical proposal, step (b) and/or step (d) roasting preferred 400-600 DEG C of temperature, roasting when
Between preferably 1-8 hours.
And wherein described macropore Si-Al oxide carriers can be prepared using method of the prior art or from commercially available canal
Road is obtained.If using self-control, can be, but not limited to using the preparation method comprised the following steps：
(1), taking polyethylene glycol 1400~1600, polyethylene glycol 1900~2100 and the fusing of epoxy resin Hybrid Heating, acute
During strong stirring, diethylenetriamine is rapidly added, reaction liquid is moved into crystallizing kettle, in 60~80 DEG C of 3~5h of crystallization, obtained
To Off-white solid, cyclic washing removes polyethylene glycol, porous polymer template β is obtained after drying.
(2), tetraethyl orthosilicate and aluminium isopropoxide are dissolved in ethanol according to required Si/Al mol ratios, added many
Pore polymer template β, is well mixed, ammoniacal liquor is added with vigorous stirring, filters out sediment, dries, is calcined, most
Spin, extrusion are used afterwards or sheetmolding is beaten, and obtain big pore Si-Al oxide carriers of the present invention.
The preparation method of embodiment part macropore Si-Al oxides is specific as follows：Take 90 grams of polyethylene glycol 1500s,
70 grams of polyethylene glycol 2000s and 80 grams of epoxy resin Hybrid Heating fusings, when being stirred vigorously, are rapidly added 20 grams of diethyls
Alkene triamine, reaction liquid is moved into crystallizing kettle, in 70 DEG C of crystallization 4h, Off-white solid is obtained, with repeatedly after taking-up
Washing removes polyethylene glycol, and porous polymer template β is obtained after drying.Again by 208 grams of tetraethyl orthosilicates and 204g
Aluminium isopropoxide is dissolved in 500ml ethanol (mol ratio Si/Al=1), adds 100 grams of porous polymer template β, mixing
Uniformly, 400ml ammoniacal liquor is added with vigorous stirring, sediment is filtered out, and drying, 800 DEG C of roasting 2h obtain carrier.Through
The test of mercury method is dripped, the average pore size of carrier is 1.2 microns.
To solve the three of above-mentioned technical problem, technical scheme is as follows：
Methacrylaldehyde and synthesis of conjugated carboxylic alkeneacid, in the above-mentioned technical solutions in the presence of catalyst described in any one, with water
Steam is diluent, and the oxidant reaction of propylene and the oxygen containing simple substance obtains methacrylaldehyde and acrylic acid.
It is catalyst in the key of the present invention, in the case where the present invention discloses the catalyst, those skilled in the art can
With reasonable selection oxidant and process conditions without paying creative work, as non limiting example, for example but not
It is limited to：
(1) in above-mentioned technical proposal, described oxidant is air.
(2) 330~400 DEG C of reaction temperature.
(3) with volume basis reaction raw materials composition for propylene:Air:Water vapour=1:(6~10):(1~3).
(4) reaction raw materials volume space velocity is 800~1600 hours-1。
Methacrylaldehyde and acid are prepared for Selective Oxidation of Propylene using the catalyst of the present invention, is 370 DEG C, instead in reaction temperature
It is 1400 hours to answer air speed-1Under conditions of, after 1000 hours, its propylene conversion is up to 99.1%, methacrylaldehyde and third
Olefin(e) acid total recovery is up to 92.8%, and product propylene aldehyde yield achieves preferable technique effect up to 78.1%.
In embodiments given below, it is to the investigation appreciation condition of catalyst：
Reactor：Fixed bed reactors, 25.4 millimeters of internal diameter, 1200 millimeters of reactor length
Catalyst filling amount：200 grams
Reaction temperature：380℃
Reaction time：4 hours
Volume feed：Propylene:Air:Water vapour=1:7:2
Raw material cumulative volume air speed：1000 hours-1
Reaction product is absorbed with 0 DEG C of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance (95~
105) it is valid data during %.
Propylene conversion, the definition of product yield and selectivity are：
The present invention has excellent catalytic performance and radiating effect using the carried catalyst with a large amount of macroporous structures, especially
It further prepares catalyst using the method described in two technical scheme of above-mentioned technical problem, makes catalyst in aldehyde and acid
Very excellent effect is obtained in terms of total recovery and propylene conversion, be can be used in methacrylaldehyde industrial production.
Below by embodiment, the present invention is further elaborated：
Embodiment
Embodiment 1
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 46.2 grams of ferric nitrate (Fe (NO3)3·9H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O)、
0.51 gram of potassium hydroxide (KOH) is dissolved and is stirred vigorously, and adjusts the pH=5 of solution with ammoniacal liquor, obtains aqueous dispersion.
451.6g macropore Si-Al oxide carriers are added into above-mentioned aqueous dispersion, and are transferred in Rotary Evaporators, until water
Part is evaporated, and moves into oven overnight and dries, and last 500 DEG C of roastings obtain required catalyst for 2 hours.By the master of catalyst
Want preparation technology and catalyst to constitute and be listed in table 1, the investigation result of catalyst is listed in table 2.
Embodiment 2
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O) and 10.1g ammonium molybdate ((NH4)6Mo7O24·4H2O) (mol ratio Mo:Fe=0.5 it is) molten
Yu Shuizhong, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.451.6g macropores Si-Al is added into the above-mentioned aqueous solution
Oxide carrier, and pour into Rotary Evaporators, until aqueous solution I is evaporated completely, moves into oven overnight and dry, then
500 DEG C are calcined 2 hours in Muffle furnace, obtain catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 189.9 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) dissolving
And be stirred vigorously, and the pH=5 of solution is adjusted with ammoniacal liquor, aqueous dispersion II is obtained, all catalyst precarsors are added,
And be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, last 500 DEG C of roastings obtain institute in 2 hours
The catalyst stated.Main preparation technology and the catalyst composition of catalyst are listed in table 1, the investigation result row of catalyst
In table 2.
Embodiment 3
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O) and 20.2g ammonium molybdate ((NH4)6Mo7O24·4H2O) (mol ratio Mo:Fe=1 it is) molten
Yu Shuizhong, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.451.6g macropores Si-Al is added into the above-mentioned aqueous solution
Oxide carrier, and pour into Rotary Evaporators, until aqueous solution I is evaporated completely, moves into oven overnight and dry, then
500 DEG C are calcined 2 hours in Muffle furnace, obtain catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 179.8 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) dissolving
And be stirred vigorously, and the pH=5 of solution is adjusted with ammoniacal liquor, aqueous dispersion II is obtained, all catalyst precarsors are added,
And be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, last 500 DEG C of roastings obtain institute in 2 hours
The catalyst stated.Main preparation technology and the catalyst composition of catalyst are listed in table 1, the investigation result row of catalyst
In table 2.
Embodiment 4
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O) and 28.3g ammonium molybdate ((NH4)6Mo7O24·4H2O) (mol ratio Mo:Fe=1.4 it is) molten
Yu Shuizhong, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.451.6g macropores Si-Al is added into aqueous solution I
Oxide carrier, and be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, then 500 DEG C in Muffle furnace
Roasting 2 hours, obtains catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 171.7 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) dissolving
And be stirred vigorously, and the pH=5 of solution is adjusted with ammoniacal liquor, aqueous dispersion II is obtained, all catalyst precarsors are added,
And be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, last 500 DEG C of roastings obtain institute in 2 hours
The catalyst stated.Main preparation technology and the catalyst composition of catalyst are listed in table 1, the investigation result row of catalyst
In table 2.
Embodiment 5
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O) and 40.4 ammonium molybdate ((NH4)6Mo7O24·4H2O) (mol ratio Mo:Fe=2) it is dissolved in
In water, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.451.6g macropores Si-Al is added into the above-mentioned aqueous solution
Oxide carrier, and pour into Rotary Evaporators, until aqueous solution I is evaporated completely, moves into oven overnight and dry, then
500 DEG C are calcined 2 hours in Muffle furnace, obtain catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 159.6 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) dissolving
And be stirred vigorously, and the pH=5 of solution is adjusted with ammoniacal liquor, aqueous dispersion II is obtained, all catalyst precarsors are added,
And be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, last 500 DEG C of roastings obtain institute in 2 hours
The catalyst stated.Main preparation technology and the catalyst composition of catalyst are listed in table 1, the investigation result row of catalyst
In table 2.
Embodiment 6
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O) and 101g ammonium molybdate ((NH4)6Mo7O24·4H2O) (mol ratio Mo:Fe=5) it is dissolved in
In water, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.451.6g macropores Si-Al is added into the above-mentioned aqueous solution
Oxide carrier, and pour into Rotary Evaporators, until aqueous solution I is evaporated completely, moves into oven overnight and dry, then
500 DEG C are calcined 2 hours in Muffle furnace, obtain catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 99 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) dissolving
And be stirred vigorously, and the pH=5 of solution is adjusted with ammoniacal liquor, aqueous dispersion II is obtained, all catalyst precarsors are added,
And be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, last 500 DEG C of roastings obtain institute in 2 hours
The catalyst stated.Main preparation technology and the catalyst composition of catalyst are listed in table 1, the investigation result row of catalyst
In table 2.
Embodiment 7
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O it is) soluble in water, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.To the above-mentioned aqueous solution
Middle addition 451.6g macropore Si-Al oxide carriers, and pour into Rotary Evaporators, until aqueous solution I is evaporated completely,
Move into oven overnight dry, then in Muffle furnace 500 DEG C be calcined 2 hours, obtain catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) dissolving
And be stirred vigorously, and the pH=5 of solution is adjusted with ammoniacal liquor, aqueous dispersion II is obtained, all catalyst precarsors are added,
And be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, last 500 DEG C of roastings obtain institute in 2 hours
The catalyst stated.Main preparation technology and the catalyst composition of catalyst are listed in table 1, the investigation result row of catalyst
In table 2.
Embodiment 8
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 200g ammonium molybdate
((NH4)6Mo7O24·4H2O it is) soluble in water, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.To above-mentioned water
451.6g macropore Si-Al oxide carriers are added in solution, and are poured into Rotary Evaporators, until aqueous solution I steams completely
It is dry, move into oven overnight and dry, then in Muffle furnace 500 DEG C be calcined 2 hours, obtain catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrate (Co (NO3)2·6H2O)、
69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) is dissolved and is stirred vigorously, and uses ammonia
Water adjusts the pH=5 of solution, obtains aqueous dispersion II, adds all catalyst precarsors, and be transferred to Rotary Evaporators
In, moisture content is evaporated, oven overnight is moved into and dries, last 500 DEG C of roastings obtain described catalyst for 2 hours.Will catalysis
Main preparation technology and the catalyst composition of agent are listed in table 1, and the investigation result of catalyst is listed in table 2.
Embodiment 9
In the dispensing equipped with stirring motor is filled, 200ml deionized waters (100 DEG C) are added, will be by 171.7 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 36.6 grams of bismuth nitrate (Bi (NO3)3·5H2O), 49.5 grams of cobalt nitrates
(Co(NO3)2·6H2O), 69.3 grams of nickel nitrate (Ni (NO3)2·6H2O), 0.51 gram of potassium hydroxide (KOH) dissolving
And be stirred vigorously, and the pH=5 of solution is adjusted with ammoniacal liquor, aqueous dispersion II is obtained, 451.6g is added into aqueous dispersion II
Macropore Si-Al oxide carriers, and be transferred in Rotary Evaporators, moisture content is evaporated, oven overnight is moved into and dries, then
500 DEG C are calcined 2 hours in Muffle furnace, obtain catalyst precarsor.
In the dispensing equipped with stirring motor is filled, 100ml deionized waters (100 DEG C) are added, by 46.2 grams of ferric nitrates
(Fe(NO3)3·9H2O) and 28.3g ammonium molybdate ((NH4)6Mo7O24·4H2O) (mol ratio Mo:Fe=1.4 it is) molten
Yu Shuizhong, the pH=5 of solution is adjusted with ammoniacal liquor, aqueous solution I is obtained.All catalyst precarsors are added, and are transferred to rotation
Turn in evaporimeter, be evaporated moisture content, move into oven overnight and dry, last 500 DEG C of roastings obtain described catalyst for 2 hours.
Main preparation technology and the catalyst composition of catalyst are listed in table 1, the investigation result of catalyst is listed in table 2.
Table 1, catalyst composition and preparation condition
Table 2, catalyst investigate result
Claims (10)
1. for synthesis of acrolein and the catalyst of acrylic acid, including following components in terms of parts by weight：
Macropore Si-Al oxide carriers, 35-80 parts；
Active component thereon, 20-65 parts are loaded in it；
The active component is expressed as Mo with atomicity12BiaNicQsYeZfOx；
Wherein Q is selected from least one of Mg, Co, Ca, Be, Cu, Zn, Pb, Mn, Fe；Y be selected from
At least one of K, Rb, Na, Li or Cs；Z is at least one of La, Ce or Sm；A is Bi atomicities；
C is Ni atomicities；S is Q atomicities；E is Y atomicities；F is Z atomicities；X is to meet other element compounds
Oxygen atom sum needed for valency.
2. catalyst according to claim 1, it is characterized in that a span is 0.05~6.0.
3. catalyst according to claim 1, it is characterized in that c span is 0.05~6.0.
4. catalyst according to claim 1, it is characterized in that s span is 0.05~6.0.
5. catalyst according to claim 1, it is characterized in that e span is 0~0.5.
6. catalyst according to claim 1, it is characterized in that f span is 0~5.0.
7. catalyst according to claim 1, it is characterized in that the average hole of described macropore Si-Al oxide carriers
Footpath is 0.5-2.5 microns.
8. catalyst according to claim 1, it is characterized in that the Si/Al of described macropore Si-Al oxide carriers
Mol ratio 0.5~3.
9. methacrylaldehyde and synthesis of conjugated carboxylic alkeneacid, in the presence of the catalyst as described in any one of claim 1~8, with
Water vapour is diluent, and the oxidant reaction of propylene and the oxygen containing simple substance obtains methacrylaldehyde and acrylic acid.
10. method according to claim 9, it is characterized in that described oxidant is air.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111068699A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst suitable for producing acrolein and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN1564709A (en) * | 2002-05-16 | 2005-01-12 | Lg化学株式会社 | Method for preparing a catalyst for partial oxidation of propylene |
| CN104275192A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrolein and acrylic acid and preparation method and application thereof |
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- 2016-04-13 CN CN201610227758.8A patent/CN107282057B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1258567A (en) * | 1998-12-30 | 2000-07-05 | 中国石油化工集团公司 | Macroporous Alpha-alumina and its preparation and application |
| CN1564709A (en) * | 2002-05-16 | 2005-01-12 | Lg化学株式会社 | Method for preparing a catalyst for partial oxidation of propylene |
| CN104275192A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Catalyst for synthesis of acrolein and acrylic acid and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111068699A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Catalyst suitable for producing acrolein and use thereof |
| CN111068699B (en) * | 2018-10-18 | 2023-05-02 | 中国石油化工股份有限公司 | Catalyst suitable for producing acrolein and application thereof |
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