CN109304190A - Glycerol acrolein catalyst - Google Patents
Glycerol acrolein catalyst Download PDFInfo
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- CN109304190A CN109304190A CN201710628232.5A CN201710628232A CN109304190A CN 109304190 A CN109304190 A CN 109304190A CN 201710628232 A CN201710628232 A CN 201710628232A CN 109304190 A CN109304190 A CN 109304190A
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- glycerol
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- methacrylaldehyde
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
-
- 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
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the preparation methods and the application in terms of glycerol prepares methacrylaldehyde of glycerol acrolein catalyst and its catalyst, mainly solve the problems, such as that catalyst methacrylaldehyde yield is relatively low in the prior art, by using glycerol acrolein catalyst, active constituent includes Nb2O5And P2O5, and the molar ratio of P and Nb is the technical solution greater than 0 and less than 15, preferably solves the technical problem, can be used in the industrial production of glycerol acrolein.
Description
Technical field
The present invention relates to glycerol acrolein catalyst more particularly to a kind of catalyst for dehydrating glycerin and its should
The preparation method of catalyst and the application in terms of glycerol prepares methacrylaldehyde.
Background technique
Methacrylaldehyde is a kind of unsaturated aldehyde compound, due to wherein simultaneously containing unsaturated double bond and carbonyl, having
High chemical reactivity is the intermediate of multi-chemical.Most of methacrylaldehyde is for selective oxidation preparation third
Olefin(e) acid, World Propylene acid annual output has been up to 7,700,000 tons within 2015.
Methacrylaldehyde is mainly to be aoxidized by the selective vapor of propylene come what is prepared, and propylene source is mainly that petroleum is split at present
Solution production, however, with the reduction of fossil feedstock and the increase of environmental protection pressure, how using reproducible raw material substitution fossil
The correlative study that raw material prepares chemicals is more and more, and the natural by-product glycerol especially obtained from biodiesel oil product is
Raw material prepares methacrylaldehyde and receives great attention.
The research that a large amount of dehydrating glycerins prepare methacrylaldehyde is reported that patent CN101070276A such as is reported with acidity point
Son sieve be catalyst, 200-500 DEG C, pressure 0.001-3.0MPa, liquid air speed 0.1-100h-1, acrylic acid yield is up to 70-
80%, but molecular sieve catalyst has that high-temperature water is hot poor: patent CN102936190A, CN102936189A,
CN102942462A, using pyridine, imidazoles and quaternary ammonium salt ionic liquid as catalyst, at 250-350 DEG C of reaction temperature, ion
The molar ratio of liquid and glycerol is to prepare methacrylaldehyde by glycerol liquid-phase dehydration, the conversion ratio of glycerol is under 0.1:100-1.5:100
100%, the yield of product propylene aldehyde is 30.5-68.2%, but ionic-liquid catalyst higher cost, production efficiency are also not so good as
The problems such as fixed bed reactors are high.105498845 A of patent CN uses a kind of supercritical CO2The CsPW/Zr- prepared in environment
MCM-41 catalyst reaches 65.2~100% using the catalyst glycerol conversion yield, and acrolein selectivity reaches 56.8~
85.4%, but super critical condition the high requirements on the equipment, investment are big.
But the catalyst methacrylaldehyde yield of the prior art is relatively low.
Summary of the invention
The first technical problem to be solved by the present invention is the relatively low problem of catalyst methacrylaldehyde yield in the prior art,
A kind of novel dehydration catalyst is provided, which can efficiently convert methacrylaldehyde for the glycerol of non-petroleum sources, and
Has the characteristics that methacrylaldehyde high income.
The second technical problem to be solved by the present invention is to provide the preparation side of catalyst described in one of above-mentioned technical problem
Method.
It is de- in glycerol that the third technical problem to be solved by the present invention is to provide catalyst described in one of above-mentioned technical problem
The aquatic application for producing methacrylaldehyde.
One of to solve above-mentioned technical problem, technical scheme is as follows:
Glycerol acrolein catalyst, active constituent include Nb2O5And P2O5, and the molar ratio of P and Nb is greater than 0
And less than 15.
In above-mentioned technical proposal, as non limiting example, the molar ratio of the P and Nb can be 0.1,0.2,0.3,
0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.01,1.1,2,3,4,5,6,7,8,9,10,11,12,13,14 etc..
In above-mentioned technical proposal, it is also preferable to include BeO for the active constituent, at this point, Be and Nb is improving methacrylaldehyde yield
Aspect has synergistic effect.
In above-mentioned technical proposal, the molar ratio of Be and Nb are preferably 0.01~10, such as, but not limited to 0.05,0.1,
0.25,0.30,0.35,0.40,0.43,0.5,1,1.5,2,2.5,3,3.5,4,5,6,7,8,9 etc..But further preferred Be
Molar ratio with Nb is preferably 0.1~0.5.
In above-mentioned technical proposal, when the active constituent includes simultaneously Nb2O5And P2O5When with BeO, the active constituent packet
Include the composite oxides indicated using following general formula:
NbBeaPbOx
Wherein, a be Be and Nb molar ratio, be 0~10, such as, but not limited to 0.05,0.1,0.25,0.30,0.35,
0.40,0.43,0.5,1,1.5,2,2.5,3,3.5,4,5,6,7,8,9 etc..But the molar ratio of further preferred Be and Nb is excellent
It is selected as 0.1~0.5；B is the molar ratio of P and Nb, and b:(2a/3+1) be greater than 0 and less than 15, more preferably greater than 0 and 1.2 hereinafter,
Can be 0.1 as non limiting example, 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.01,1.1,2,3,4,
5,6,7,8,9,10,11,12,13,14 etc.；X is oxygen atom total moles needed for meeting other element valences.
In above-mentioned technical proposal, as the most preferred technical solution, a is 0.1~0.5 and b:(2a/3+1) it is greater than 0
And 1.2 or less.
In above-mentioned technical proposal, the catalyst may include carrier, can not also include carrier.
In above-mentioned technical proposal, when using carrier, those skilled in the art can reasonably select and be not required to pay creation
Property labour, and can obtain comparable technical effect.The such as, but not limited to described carrier be selected from aluminium oxide, silica, titanium oxide,
At least one of molecular sieve, rare earth oxide, active carbon, graphene and clay.
To solve above-mentioned technical problem two, technical solution of the present invention is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, includes the following steps:
(1) it is mixed containing niobium compound with phosphorus-containing compound；
(2) it roasts.
In above-mentioned technical proposal, when the active constituent includes BeO, preparation method specific manifestation is as follows:
(1) containing niobium compound, phosphorus-containing compound and containing beryllium compound mixing；
(2) it roasts.
In above-mentioned technical proposal, there can be the step of crystallization between step (2) and step (1), the step after crystallization
(2) there can also be dry step before.
In above-mentioned technical proposal, mixture the step of preferably comprising crystallization that step (1) obtains, the mixture after crystallization is
It is roasted.Optional 90~150 DEG C of the temperature of crystallization (such as, but not limited to 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C, 115 DEG C, 120
DEG C, 125 DEG C, 130 DEG C, 135 DEG C, 140 DEG C, 145 DEG C etc.), the time of crystallization optional 5~40 hours (such as, but not limited to 10
Hour, 15 hours, 20 hours, 24 hours, 30 hours, 35 hours etc.).
In above-mentioned technical proposal, the temperature of roasting is preferably 200-1000 DEG C, and more preferable 400~700 DEG C, for example (,) but it is unlimited
In 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C.
In above-mentioned technical proposal, the time of roasting is preferably 0.5-100 hours.Such as, but not limited to 1 hour, 1.5 hours,
2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours,
7.5 hours, 8 hours, 8.5 hours, 9 hours, 10 hours, 20 hours, 30 hours, more preferable 3~10 hours.
In above-mentioned technical proposal, the atmosphere of roasting preferably is selected from oxidizing atmosphere, reducing atmosphere or inert atmosphere.
In above-mentioned technical proposal, the oxidizing atmosphere is for example but not limited in vapor or oxygenous atmosphere extremely
Few one kind.The oxygenous atmosphere can for example be but not limited to the mixture of oxygen, air, oxygen and N2, oxygen with it is lazy
At least one of the mixture of property gas；The preferably oxygenous atmosphere of the oxidizing atmosphere, in order to which economic consideration is oxygenous
The preferred air of atmosphere.
For above-mentioned technology according in scheme, inert atmosphere is selected from least one of nitrogen and inert gas, the inert gas
Such as, but not limited to selected from least one of He, Ne and Ar.
In above-mentioned technical proposal, as to the non limiting example containing niobium compound, niobium oxalate, tartaric acid niobium can be
Deng.
In above-mentioned technical proposal, as the non limiting example to phosphorus-containing compound, phosphoric acid, pyrophosphoric acid, more can be
The normal salt or acid salt of polyphosphoric acid and above-mentioned acid, for example, they ammonium salt (such as, but not limited to ammonium phosphate, monoammonium phosphate,
Ammonium dihydrogen phosphate) etc..
In above-mentioned technical proposal, as to the non limiting example containing beryllium compound, beryllium nitrate, beryllium sulfate can be
Deng.
The key point of catalyst of the present invention does not lie in the geometry and size of catalyst, thus to the shape of catalyst and
Size is not particularly limited, and the various shape and size of existing carrier are used equally for the present invention and obtain year-on-year result.Such as
Catalyst of the invention can take spherical, Raschig ring or cylinder etc..Preferable 3~the 5mm of spherical diameter；Raschig ring outer diameter can
It is preferred that 4~7mm, internal diameter preferably 1.5~3mm, length preferably 3~5mm；Preferable 4~the 7mm of cylindrical outer diameter, length preferably 3~
5mm。
Catalyst of the present invention does not have molding mode special, can select those of commonly used in the art such as but unlimited
In carrying out spin, extrusion or beat piece etc.；Shaping assistant needed for art technology person can also reasonably select molding.
To solve above-mentioned technical problem three, technical scheme is as follows:
Catalyst described in any one of described technical solution of one of above-mentioned technical problem is in glycerin catalytic dehydration system
Make the purposes in methacrylaldehyde.
Specific application method may is that
The synthetic method of methacrylaldehyde, including catalyst described in any one of glycerinated raw material and above-mentioned technical proposal connect
Touching, glycerol occur dehydration and generate methacrylaldehyde.It is catalyst in key of the invention, discloses the catalyst in the present invention
In the case of, those skilled in the art can reasonably select oxidant and process conditions without making the creative labor, as
Non limiting example, such as, but not limited to:
Preferably 200~550 DEG C of reaction temperature, more preferable 250~350 DEG C.
Pressure preferably 0.1~100bar, more preferable 0.1~50bar.If not particularly pointed out in the present invention, the pressure
It is gauge pressure.
Reactor does not have specific limitation, can use autoclave, fixed bed or fluidized-bed reactor, it is contemplated that production efficiency
And catalyst life, preferred fixed bed catalyst.
In above-mentioned technical proposal, the glycerinated raw material can also contain solvent, and the solvent can be water, C6~C20
Hydrocarbon, the hydrocarbon can be alkane or aromatic hydrocarbons.
When glycerinated raw material when containing solvent, the concentration of glycerol is not particularly limited, those skilled in the art can close
Reason selection, such as, but not limited to by weight, the concentration 10~70% of glycerol in raw material, such as 15%, 20%, 25%, 30%,
35%, 40%, 45% etc..More preferable 20~50%.
In above-mentioned technical proposal, the air speed of raw material is not particularly limited, and those skilled in the art can reasonably select, such as
But it is not limited to unstrpped gas volume space velocity 100~5000 hours-1, 500-2000 hours more preferable-1。
In embodiments given below, to the investigation evaluation condition of catalyst are as follows:
Reactor: fixed bed reactors, 25.4 millimeters of internal diameter, 1500 millimeters of reactor length
Catalyst filling amount: 200ml
Glycerine water solution mass concentration: 30%
Reaction temperature: 330 DEG C (glycerine water solution has gasified at this time)
Raw material total volume air speed (including water and glycerol): 1000 hours-1
Reaction time: 2000h
Reaction product is dissolved in diluted acid in 1L deionized water with 0 and absorbs, with gas chromatographic analysis product.And it is flat to calculate carbon
Weighing apparatus is valid data when Carbon balance is in (95~105) %.
Glycerol conversion yield and product yield is defined as:
Using catalyst of the invention, the yield of methacrylaldehyde is up to 70% or more, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated:
Specific embodiment
Embodiment 1:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L deionized water, 1mol diammonium hydrogen phosphate
((NH4)2HPO4) be dissolved in 1L deionized water, then two solution are quickly mixed, and 120 DEG C crystallization 24 hours, it is spraying dry
It is dry to obtain catalyst precursor, it is roasted 4 hours using 500 DEG C, obtains phosphate niobium catalyst.
100g phosphate niobium catalyst powder, 5g graphite are taken, 10g deionized water is beaten sheetmolding and prepared after evenly mixingRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 2:
Respectively by 1.5mol beryllium nitrate (Be (NO3)2·3H2O it) is dissolved in 1L deionized water, 1mol diammonium hydrogen phosphate
((NH4)2HPO4) be dissolved in 1L deionized water, then two solution are quickly mixed, and 120 DEG C crystallization 24 hours, it is spraying dry
It is dry to obtain catalyst precursor, it is roasted 4 hours using 500 DEG C, obtains beryllium phosphate catalyst.
100g beryllium phosphate catalyst fines, 5g graphite are taken, 10g deionized water is beaten sheetmolding and prepared after evenly mixingRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 3:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O), 0.1mol beryllium nitrate (Be (NO3)2·3H2O) it is dissolved in 1L
In deionized water, 1.07mol diammonium hydrogen phosphate ((NH4)2HPO4) be dissolved in 1L deionized water, then two solution are quickly mixed
Close, and 120 DEG C crystallization 24 hours, spray drying obtain catalyst precursor, using 500 DEG C roast 4 hours, obtain niobium-
Beryllium compound phosphoric acid salt catalyst.
Take 100g niobium-beryllium composite phosphate catalyst fines, 5g graphite, 10g deionized water, after evenly mixing, beat piece at
Type is preparedRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 4:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O), 0.25mol beryllium nitrate (Be (NO3)2·3H2O it) is dissolved in
In 1L deionized water, 1.17mol diammonium hydrogen phosphate ((NH4)2HPO4) be dissolved in 1L deionized water, it is then that two solution are quick
Mixing, and 120 DEG C crystallization 24 hours, spray drying obtain catalyst precursor, using 500 DEG C roast 4 hours, obtain
Niobium-beryllium compound phosphoric acid salt catalyst.
Take 100g niobium-beryllium composite phosphate catalyst fines, 5g graphite, 10g deionized water, after evenly mixing, beat piece at
Type is preparedRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 5:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O), 0.43mol beryllium nitrate (Be (NO3)2·3H2O it) is dissolved in
In 1L deionized water, 1.29mol diammonium hydrogen phosphate ((NH4)2HPO4) be dissolved in 1L deionized water, it is then that two solution are quick
Mixing, and 120 DEG C crystallization 24 hours, spray drying obtain catalyst precursor, using 500 DEG C roast 4 hours, obtain
Niobium-beryllium compound phosphoric acid salt catalyst.
Take 100g niobium-beryllium composite phosphate catalyst fines, 5g graphite, 10g deionized water, after evenly mixing, beat piece at
Type is preparedRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 6:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O), 1mol beryllium nitrate (Be (NO3)2·3H2O) 1L is dissolved in go
In ionized water, 2mol diammonium hydrogen phosphate ((NH4)2HPO4) be dissolved in 1L deionized water, then two solution are quickly mixed, and
120 DEG C crystallization 24 hours, spray drying obtain catalyst precursor, using 500 DEG C roast 4 hours, it is compound to obtain niobium-beryllium
Phosphate catalyst.
Take 100g niobium-beryllium composite phosphate catalyst fines, 5g graphite, 10g deionized water, after evenly mixing, beat piece at
Type is preparedRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 7:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O), 2.3mol beryllium nitrate (Be (NO3)2·3H2O) it is dissolved in 1L
In deionized water, 2mol diammonium hydrogen phosphate ((NH4)2HPO4) be dissolved in 1L deionized water, then two solution are quickly mixed,
And 120 DEG C crystallization 24 hours, spray drying obtain catalyst precursor, using 500 DEG C roast 4 hours, it is multiple to obtain niobium-beryllium
Close phosphate catalyst.
Take 100g niobium-beryllium composite phosphate catalyst fines, 5g graphite, 10g deionized water, after evenly mixing, beat piece at
Type is preparedRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 8:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O), 4mol beryllium nitrate (Be (NO3)2·3H2O) 5L is dissolved in go
In ionized water, 1.83mol diammonium hydrogen phosphate ((NH4)2HPO4) be dissolved in 1L deionized water, then two solution are quickly mixed,
And 120 DEG C crystallization 24 hours, spray drying obtain catalyst precursor, using 500 DEG C roast 4 hours, it is multiple to obtain niobium-beryllium
Close phosphate catalyst.
Take 100g niobium-beryllium composite phosphate catalyst fines, 5g graphite, 10g deionized water, after evenly mixing, beat piece at
Type is preparedRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Embodiment 9:
Respectively by 1mol niobium oxalate (Nb (HC2O4)5·6H2O), 9mol beryllium nitrate (Be (NO3)2·3H2O) 5L is dissolved in go
In ionized water, 2.1mol diammonium hydrogen phosphate ((NH4)2HPO4) be dissolved in 1L deionized water, then two solution are quickly mixed,
And 120 DEG C crystallization 24 hours, spray drying obtain catalyst precursor, using 500 DEG C roast 4 hours, it is multiple to obtain niobium-beryllium
Close phosphate catalyst.
Take 100g niobium-beryllium composite phosphate catalyst fines, 5g graphite, 10g deionized water, after evenly mixing, beat piece at
Type is preparedRaschig ring catalyst particle, catalytic activity is shown in Table 1.
Table 1: different catalysts appraisal result
Claims (9)
1. glycerol acrolein catalyst, active constituent include Nb2O5And P2O5, and the molar ratio of P and Nb is greater than 0 and small
In 15.
2. catalyst according to claim 1, it is characterized in that further including carrier.
3. catalyst according to claim 2, it is characterized in that the carrier is selected from aluminium oxide, silica, titanium oxide, molecule
At least one of sieve, rare earth oxide, active carbon, graphene and clay.
4. the preparation method of catalyst described in claim 1, includes the following steps:
(1) it is mixed containing niobium compound with phosphorus-containing compound；
(2) it roasts.
5. preparation method according to claim 1, it is characterized in that 200-1000 DEG C of temperature of roasting.
6. preparation method according to claim 1, it is characterized in that the time of roasting is 0.5-100 hours.
7. preparation method according to claim 1, it is characterized in that the atmosphere of roasting is selected from oxidizing atmosphere, reducing atmosphere
Or inert atmosphere.
8. preparation method according to claim 1, it is characterized in that the oxidizing atmosphere is air.
9. purposes of the catalyst described in any one of claims 1 to 3 in glycerin catalytic dehydration manufacture methacrylaldehyde.
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| IN SUN CHO ET AL: "Electronic Band Structure, Optical Properties, and Photocatalytic Hydrogen Production of Barium Niobium Phosphate Compounds (BaO–Nb2O5–P2O5)", 《EUR. J. INORG. CHEM.》 * |
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