CN109304162A - Glycerol production acrylic acid - Google Patents
Glycerol production acrylic acid Download PDFInfo
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- CN109304162A CN109304162A CN201710628240.XA CN201710628240A CN109304162A CN 109304162 A CN109304162 A CN 109304162A CN 201710628240 A CN201710628240 A CN 201710628240A CN 109304162 A CN109304162 A CN 109304162A
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6484—Niobium
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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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- 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
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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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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Abstract
The present invention relates to glycerol production acrylic acids, mainly solve the problems, such as that acrylic acid yield is relatively low in prior art glycerol acrylic acid synthesizing process, by using glycerol production acrylic acid, it is contacted including glycerinated raw material and oxygenous raw material with catalyst, glycerol occurs dehydration and generates methacrylaldehyde, and methacrylaldehyde is further oxidized to acrylic acid；The catalyst, including carrier and active component, the active component include the technical solution selected from least one of Pt, Re and Rh, preferably solve the technical problem, can be used in the industrial production of glycerol acrylic acid synthesizing.
Description
Technical field
The present invention relates to glycerol production acrylic acids.
Background technique
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 for synthesizing advanced water-absorbing resins and water treatment agent etc., and a part of acrylic acid is used for being esterified
To manufacture the esters of acrylic acid such as methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-EHA, and propylene
Acid ester polymer is mainly used in the fields such as adhesive, coating, weaving, plastics, leather, papermaking.
Acrylic acid and its series of products, are rapidly developed in recent years, and 2015, acrylicacidandesters class whole world total output
7,700,000 t/a are had reached, 6,070,000 t/a compared with the end of the year in 2013 increase about 27%, and the process units of acrylic acid is mainly concentrated at present
In the U.S., Europe, Japan and China, wherein China is the country that acrylic acid production capacity is with fastest developing speed in recent years, China is same within 2012
When be more than US and European, have become the maximum country of acroleic acid device production capacity in the world.Whole world industrial production acrylic acid
Large-scale plant all use propylene oxidation technology, which has had the history of decades, and a large amount of technological development makes its production
Technique is gradually improved.However, how to be substituted using reproducible raw material with the reduction of fossil feedstock and the increase of environmental protection pressure
The correlative study that fossil feedstock prepares chemicals is more and more, and the natural by-product especially obtained from biodiesel oil product is sweet
Oil prepares acrylic acid for raw material and receives great attention.
Up to now, many patent authorizings are for the catalyst related invention from methacrylaldehyde production acrylic acid method,
Wherein most of is the catalyst containing molybdenum-vanadium (Mo-V), such as Chinese patent CN 1070468C, CN 1031488A, CN
1146438A, CN 100378058C, CN 1031050C, CN 1169619C, CN 1583261A and CN 1146439A etc., this
Catalyst described in a little patents, preparation method are mostly that solution is made in more metallic compounds in the presence of solvent or water, then
Insoluble oxide is added and evaporates under heating and stirring dry, then calcines, crush and molding preparation method.And it discloses at present
Patent described in element composition differ greatly, the catalyst principal component as disclosed in Chinese patent CN 1169619C be molybdenum, vanadium and
Copper adds necessary tellurium, it is believed that tellurium can make the active phase oxidation molybdenum of this catalyst and copper molybdate more stable, Ke Yiyan
Slow catalyst causes to inactivate because of Mo loss；It is main that catalyst disclosed in Chinese patent CN 1583261A, which is by 1. molybdenum, vanadium, copper,
Active component, 2. it is essential at least by titanium and antimony stabilization component and 3. nickel, iron, silicon, aluminium, alkali metal alkaline earth metal group
At complex chemical compound；Catalyst disclosed in Chinese patent CN 1050779C its form substantially molybdenum including oxide form,
Vanadium, tungsten, copper and mickel element；Catalyst disclosed in Chinese patent CN 1146439A contain molybdenum, vanadium, copper and containing elemental tungsten, niobium,
One or more of tantalum, chromium and cerium element, and it is first in elemental tungsten, vanadium, niobium and tantalum containing copper, molybdenum and at least one
The oxo metal oxide of the HT copper molybdate structure type of element.
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 acrylic acid yield of the prior art is relatively low.
Summary of the invention
The technical problem to be solved by the present invention is to the catalyst third that dehydrating glycerin in the prior art aoxidizes acrylic acid processed
The relatively low problem of olefin(e) acid yield, provides a kind of new dehydrating glycerin and oxidation prepares acrylic acid, and this method is enough by non-petroleum
The glycerol in source is efficiently converted into acrylic acid, and has the characteristics that acrylic acid high income.
In order to solve the above technical problems, technical scheme is as follows:
Glycerol production acrylic acid is contacted including glycerinated raw material and oxygenous raw material with catalyst, glycerol
Dehydration occurs and generates methacrylaldehyde, methacrylaldehyde is further oxidized to acrylic acid；The catalyst, including carrier and active group
Point, the active component includes selected from least one of Pt, Re and Rh.
In above-mentioned technical proposal, preferably 200~550 DEG C of reaction temperature, more preferable 250~350 DEG C.
In above-mentioned technical proposal, pressure preferably 0.1~100bar, more preferable 0.1~50bar.If not special in the present invention
It points out, the pressure is gauge pressure.
In above-mentioned technical proposal, reactor does not have specific limitation, can use autoclave, fixed bed or fluidized-bed reaction
Device, it is contemplated that production efficiency and catalyst life, preferably fixed bed.
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.
In above-mentioned technical proposal, when glycerinated raw material when containing solvent, the concentration of glycerol is not particularly limited, this field
Technical staff can reasonably select, 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%.
As non limiting example, oxygen can use pure oxygen, air, oxygen-enriched, oxygen deprivation, oxygen and N2Mixture, oxygen
With noble gas mixtures, air and N2Mixture, air and noble gas mixtures etc. form.
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 the gas volume air speed of raw material 50~5000 hours-1, 80-1000 hours more preferable-1。
The molar ratio of oxygen and glycerol is not particularly limited, and those skilled in the art can rationally determine, such as but unlimited
In 0.5~5, such as, but not limited to 0.6,0.7,0.8,0.9,1.0,1.2,1.5,2,3 etc., but preferably 0.8~3.
In above-mentioned technical proposal, in catalyst the content of active constituent be preferably greater than 0g/L and 50g/L hereinafter, for example but
It is not limited to 0.1g/L, 0.5g/L, 1g/L, 5g/L, 10g/L, 15g/L, 20g/L, 30g/L, 40g/L etc..
In above-mentioned technical proposal, the carrier preferably is selected from including aluminium oxide, silica, titanium oxide, molecular sieve, rare-earth oxidation
Object, active carbon, graphene, Nb2O5、P2O5At least one of with clay.
In above-mentioned technical proposal, the carrier preferably is selected from including aluminium oxide, silica, titanium oxide, molecular sieve, rare-earth oxidation
Object, active carbon, graphene, Nb2O5、P2O5With the mixture of at least two compositions in clay.
In above-mentioned technical proposal, the carrier more preferably includes by Nb2O5And P2O5The composite oxides of composition, at this time institute
Stating composite oxides is indicated with atomic ratio measuring with following chemical formula:
NbPaOx
Wherein, a is the molar ratio of P and Nb, and x is the oxygen atomicity for meeting stoichiometric ratio, and a is greater than 0 and less than 15, most
Preferably greater than 0 and 1.2 or less.As non limiting example, a can be 0.131,0.231,0.331,0.431,0.531,
0.631,0.731,0.831,0.931,1.0,1.0131,1.131,2,3,4,5,6,7,8,9,10,11,12,13,14 etc..
In above-mentioned technical proposal, one of as a preferred technical scheme, the active constituent includes Ru and Pt simultaneously, Ru and
Pt has mutual promoting action in terms of improving acrylic acid yield.The ratio of Ru and Pt is not particularly limited, such as, but not limited to
The weight ratio of Ru and Pt is 0.0131~100, more preferable 0.131~10, be can be as unrestricted specific example
0.231,0.331,0.531,1,1.531,2.031,2.531,3,4,5,6,7,8,9 etc..
In above-mentioned technical proposal, as a preferred technical scheme two, the active constituent includes Ir and Pt simultaneously, Ir and
Pt has mutual promoting action in terms of improving acrylic acid yield.The ratio of Ir and Pt is not particularly limited, such as, but not limited to
The weight ratio of Ir and Pt is 0.0131~100, more preferable 0.131~10, be can be as unrestricted specific example
0.231,0.331,0.531,1,1.531,2.031,2.531,3,4,5,6,7,8,9 etc..
The most preferred technical solution is that affiliated active constituent includes Pt, Ru and Ir, the Ru and Ir in the presence of Pt simultaneously
There is synergistic effect in terms of improving acrylic acid yield, and three has combined effect in terms of the yield for improving acrylic acid.
Ratio between Ru, Ir and Pt is not particularly limited, such as, but not limited to by weight Ru:Ir:Pt be 1:(0.0131~
100): (0.0131~100) is further 1:(0.131~10): (0.131~10).
The catalyst that the present invention uses can be using the method preparation included the following steps:
(1) compound solution of active component is mixed with carrier；
(2) it roasts.
In above-mentioned technical proposal, the temperature of step (2) roasting is preferably 200-1000 DEG C.Such as, but not limited to 300 DEG C,
400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, more preferable 400~600 DEG C.
In above-mentioned technical proposal, the time of step (2) 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, it is 6.5 small
When, 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 mixture that step (1) is mixed to get carries out step (2) roasting preferably through dry again.
Dry temperature is preferably 50~200 DEG C, such as, but not limited to 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C,
130 DEG C etc..The dry time is preferably 1~100 hour, such as, but not limited to 5 hours, 6 hours, 8 hours, 9 hours, it is 10 small
When, 12 hours, 24 hours, 36 hours, 72 hours etc..
In above-mentioned technical proposal, the atmosphere of step (2) roasting preferably is selected from oxidizing atmosphere or inert atmosphere.Oxidizing atmosphere
It is preferred that oxygenous atmosphere, such as, but not limited to vapor, oxygen, air, oxygen-containing gas and N2 (and/or inert gas))
Mixture；Inert atmosphere select at least one of nitrogen and inert gas, the inert gas such as, but not limited to be selected from He,
At least one of Ne and Ar).
It is preferably air in order to which economic consideration step (2) roast the oxidizing atmosphere in above-mentioned technical proposal.
It include by Nb when the carrier uses2O5And P2O5When the composite oxides of composition, as non-limiting citing,
The composite oxides can be using the method preparation included the following steps:
(i) it is mixed containing niobium compound with phosphorus-containing compound；
(ii) it roasts.
In above-mentioned technical proposal, there can be the step of crystallization between step (ii) and step (i), the step after crystallization
(ii) there can also be dry step before.
In above-mentioned technical proposal, mixture the step of preferably comprising crystallization that step (i) obtains, the mixture after crystallization is
Carry out the calcination steps of (ii).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 (examples
Such as, but not limited to, 10 hours, 15 hours, 20 hours, 24 hours, 30 hours, 35 hours etc.).
In above-mentioned technical proposal, the temperature of step (ii) roasting is preferably 200-1000 DEG C, and more preferable 400~700 DEG C, example
Such as, but not limited to, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C.
In above-mentioned technical proposal, the time of step (ii) 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, it is 6.5 small
When, 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 step (ii) roasting preferably is selected from oxidizing atmosphere or inert atmosphere.(oxidisability gas
The preferably oxygenous atmosphere of atmosphere, such as, but not limited to vapor, oxygen, air, oxygen-containing gas and N2 (and/or inert gas))
Mixture；Inert atmosphere selects at least one of nitrogen and inert gas, and the inert gas is such as, but not limited to selected from
At least one of He, Ne and Ar).
It is preferably air in order to which economic consideration step (ii) roasts the oxidizing atmosphere in above-mentioned technical proposal.
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..
The key point of catalyst of the present invention does not lie in the geometry and size of carrier, therefore to the shape and size of carrier
It is not particularly limited, the various shape and size of existing carrier are used equally for the present invention and obtain year-on-year result.Such as this hair
Bright carrier can take spherical, Raschig ring or cylinder etc..Preferable 3~the 5mm of spherical diameter；Raschig ring outer diameter preferable 4
~7mm, internal diameter preferably 1.5~3mm, length preferably 3~5mm；Preferable 4~the 7mm of cylindrical outer diameter, length preferably 3~5mm.
Carrier of the present invention do not have to molding mode it is special, can select it is those of commonly used in the art, such as, but not limited to
Carry out spin, extrusion or beat piece etc.；Shaping assistant needed for art technology person can also reasonably select molding.
The compound of active component is not particularly limited.
Such as the compound of Ru can be but not limited to ruthenium trichloride, potassium perruthenate etc.；The compound of Os can be but not
It is limited to potassium osmate, osmic acid etc.；The compound of Ir can be but not limited to iridous chloride, iridic chloride, ammonium chloroiridate, six chloro-iridic acids
Potassium etc.；The compound of Pt can be but not limited to chloroplatinic acid, potassium platinic chloride, potassium chloroplatinite etc.；The compound of Au can be
But be not limited to four chloraurides etc..
The compound solution of the active component is not particularly limited using solvent, but safety and the preferred water of economic consideration is
Solvent.
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)
Volume volume space velocity after glycerol gasification: 100 hours-1
Volume of air air speed: 1000 hours1
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:
It is up to 70% or more using using the yield of catalyst of the invention, acrylic acid, achieves preferable technical effect.
Below by embodiment, the present invention is further elaborated:
Specific embodiment
Embodiment 1:
Take the commercially available SiO of 400ml2Support powder, 20g graphite, 40g deionized water beat sheetmolding after evenly mixing, and 120 DEG C
Drying, 500 DEG C roast 2 hours, prepareRaschig ring carrier granular.
3.5g platinum tetrachloride (PtCl4) be dissolved in 100g water, platinum tetrachloride aqueous solution is obtained, 200ml carrier granular is taken,
Platinum tetrachloride aqueous solution is poured into wherein, is sufficiently stirred, 120 DEG C of drying, 500 DEG C roast 2 hours, obtain catalyst, catalysis is lived
Property is shown in Table 1.
Embodiment 2:
Take the commercially available TiO of 400ml2Support powder, 20g graphite, 40g deionized water beat sheetmolding after evenly mixing, and 120 DEG C
Drying, 500 DEG C roast 2 hours, prepareRaschig ring carrier granular.
5.2g hydrate ruthenium trichloride (RuCl3·3H2O it) is dissolved in 100g water, obtains ruthenium trichloride aqueous solution, take 200ml
Ruthenium trichloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, 120 DEG C drying, 500 DEG C roast 2 hours, be catalyzed
Agent, catalytic activity are shown in Table 1.
Embodiment 3:
Take the commercially available niobium pentaoxide support powder of 400ml, 20g graphite, 40g deionized water, after evenly mixing, beat piece at
Type, 120 DEG C drying, 500 DEG C roast 2 hours, prepareRaschig ring carrier granular.
3.6g hydrated iridium trichloride (IrCl3·3H2O it) is dissolved in 100g water, obtains iridous chloride aqueous solution, take 200ml
Iridous chloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, 120 DEG C drying, 500 DEG C roast 2 hours, be catalyzed
Agent, catalytic activity are shown in Table 1.
Embodiment 4:
Take the commercially available niobium pentaoxide support powder of 400ml, 20g graphite, 40g deionized water, after evenly mixing, beat piece at
Type, 120 DEG C drying, 500 DEG C roast 2 hours, prepareRaschig ring carrier granular.
3.5g platinum tetrachloride (PtCl4) be dissolved in 100g water, platinum tetrachloride aqueous solution is obtained, 200ml carrier granular is taken,
Platinum tetrachloride aqueous solution is poured into wherein, is sufficiently stirred, 120 DEG C of drying, 500 DEG C roast 2 hours, obtain catalyst, catalysis is lived
Property is shown in Table 1.
Embodiment 5:
Take the commercially available niobium pentaoxide support powder of 400ml, 20g graphite, 40g deionized water, after evenly mixing, beat piece at
Type, 120 DEG C drying, 500 DEG C roast 2 hours, prepareRaschig ring carrier granular.
5.2g hydrate ruthenium trichloride (RuCl3·3H2O it) is dissolved in 100g water, obtains ruthenium trichloride aqueous solution, take 200ml
Ruthenium trichloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, 120 DEG C drying, 500 DEG C roast 2 hours, be catalyzed
Agent, catalytic activity are shown in Table 1.
Comparative example:
Take the commercially available phosphorus pentoxide support powder of 400ml, 20g graphite, 40g deionized water occurs in mixed process violent
Exothermic reaction can not form, and stop catalyst preparation.
Embodiment 6:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L 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, it is spraying dry
It is dry to obtain carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.0OxPowder.Take 400ml support powder, 20g stone
Ink, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepare
Molding Raschig ring carrier granular.
5.2g hydrate ruthenium trichloride (RuCl3·3H2O it) is dissolved in 100g water, obtains ruthenium trichloride aqueous solution, take
200mlNbP1.0OxRuthenium trichloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, 120 DEG C of drying, and 500 DEG C of roastings 2 are small
When, catalyst is obtained, catalyst activity is shown in Table 1.
Embodiment 7:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L 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, it is spraying dry
It is dry to obtain carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.0OxPowder.Take 400ml support powder, 20g stone
Ink, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepare
Molding Raschig ring carrier granular.
3.6g hydrated iridium trichloride (IrCl3·3H2O it) is dissolved in 100g water, obtains iridous chloride aqueous solution, take
200mlNbP1.0OxIridous chloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, and 120 DEG C of drying, 500 DEG C of roastings 2 are small
When, catalyst is obtained, catalyst activity is shown in Table 1.
Embodiment 8:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L 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, it is spraying dry
It is dry to obtain carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.0OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
3.5g platinum tetrachloride (PtCl4) be dissolved in 100g water, platinum tetrachloride aqueous solution is obtained, 200ml NbP is taken1.0OxIt carries
Platinum tetrachloride aqueous solution is poured into wherein, is sufficiently stirred by body particle, 120 DEG C drying, 500 DEG C roast 2 hours, obtain catalyst
Particle, catalytic activity are shown in Table 1.
Embodiment 9:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L deionized water, 1.6mol 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 carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP0.8OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
5.2g hydrate ruthenium trichloride (RuCl3·3H2O it) is dissolved in 100g water, obtains ruthenium trichloride aqueous solution, take
200mlNbP0.8OxRuthenium trichloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, and 120 DEG C of drying, 500 DEG C of roastings 2 are small
When, catalyst granules is obtained, catalytic activity is shown in Table 1.
Embodiment 10:
Respectively by 2mol 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 carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP0.5OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
5.2g hydrate ruthenium trichloride (RuCl3·3H2O it) is dissolved in 100g water, obtains ruthenium trichloride aqueous solution, take 200ml
NbP0.5OxRuthenium trichloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, 120 DEG C drying, 500 DEG C roast 2 hours, obtain
To catalyst granules, catalytic activity is shown in Table 1.
Embodiment 11:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L deionized water, 2.4mol 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 carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.2OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
5.2g hydrate ruthenium trichloride (RuCl3·3H2O it) is dissolved in 100g water, obtains ruthenium trichloride aqueous solution, take 200ml
NbP1.2OxRuthenium trichloride aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, 120 DEG C drying, 500 DEG C roast 2 hours, obtain
To catalyst granules, catalytic activity is shown in Table 1.
Embodiment 12:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L 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, it is spraying dry
It is dry to obtain carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.0OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
2.6g hydrate ruthenium trichloride (RuCl3·3H2) and 1.8g hydrated iridium trichloride (IrCl O3·3H2O) it is dissolved in 100g
In water, ruthenium trichloride-iridous chloride aqueous solution is obtained, 200ml NbP is taken1.0OxCarrier granular pours into the aqueous solution wherein,
Be sufficiently stirred, 120 DEG C drying, 500 DEG C roast 2 hours, obtain catalyst granules, catalytic activity is shown in Table 1.
Embodiment 13:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L 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, it is spraying dry
It is dry to obtain carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.0OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
2.6g hydrate ruthenium trichloride (RuCl3·3H2) and 1.75g platinum tetrachloride (PtCl O4) be dissolved in 100g water, it obtains
Ruthenium trichloride-platinum tetrachloride (PtCl4) aqueous solution, take 200ml NbP1.0OxCarrier granular pours into the aqueous solution wherein, sufficiently
Stirring, 120 DEG C drying, 500 DEG C roast 2 hours, obtain catalyst granules, catalytic activity is shown in Table 1.
Embodiment 14:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L 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, it is spraying dry
It is dry to obtain carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.0OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
1.8g hydrated iridium trichloride (IrCl3·3H2) and 1.75g platinum tetrachloride (PtCl O4) be dissolved in 100g water, it obtains
Iridous chloride-platinum tetrachloride (PtCl4) aqueous solution, take 200ml NbP1.0OxCarrier granular pours into the aqueous solution wherein, sufficiently
Stirring, 120 DEG C drying, 500 DEG C roast 2 hours, obtain catalyst granules, catalytic activity is shown in Table 1.
Embodiment 15:
Respectively by 2mol niobium oxalate (Nb (HC2O4)5·6H2O it) is dissolved in 1L 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, it is spraying dry
It is dry to obtain carrier precursor, it is roasted 4 hours using 500 DEG C, obtains NbP1.0OxSupport powder.Take 400ml support powder, 20g
Graphite, 40g deionized water beat sheetmolding after evenly mixing, 120 DEG C of drying, 500 DEG C roast 2 hours, prepareMolding Raschig ring carrier granular.
1.2g hydrated iridium trichloride (IrCl3·3H2O), 1.2g platinum tetrachloride (PtCl4) and 1.7g hydrate ruthenium trichloride
(RuCl3·3H2O it) is dissolved in 100g water, obtains iridous chloride-platinum tetrachloride-ruthenium trichloride aqueous solution, take 200ml
NbP1.0OxThe aqueous solution is poured into wherein, is sufficiently stirred by carrier granular, 120 DEG C drying, 500 DEG C roast 2 hours, be catalyzed
Agent particle, catalytic activity are shown in Table 1.
Table 1: catalytic component and appraisal result
Note: P in comparative example2O5Fail molding, therefore without further data.
Claims (10)
1. glycerol production acrylic acid is contacted including glycerinated raw material and oxygenous raw material with catalyst, glycerol hair
Raw dehydration generates methacrylaldehyde, and methacrylaldehyde is further oxidized to acrylic acid；The catalyst, including carrier and active component,
The active component includes selected from least one of Pt, Re and Rh.
2. according to the method described in claim 1, it is characterized in that reaction temperature is 200~550 DEG C.
3. according to the method described in claim 1, it is characterized in that reaction pressure is 0.1~100bar.
4. according to the method described in claim 1, it is characterized in that the glycerinated raw material contains solvent.
5. according to the method described in claim 4, it is characterized in that by weight, the concentration of glycerol is in the glycerinated raw material
10~70%.
6. according to the method described in claim 4, it is characterized in that the solvent is the hydrocarbon of water, C6~C20.
7. according to the method described in claim 6, it is characterized in that the hydrocarbon is alkane or aromatic hydrocarbons.
8. according to the method described in claim 1, it is characterized in that the gas volume air speed of raw material is 100~5000 hours-1。
9. according to the method described in claim 1, it is characterized in that further including carrier.
10. according to the method described in claim 9, it is characterized in that it includes being selected from aluminium oxide, silica, oxidation that the carrier, which is selected from,
Titanium, molecular sieve, rare earth oxide, active carbon, graphene, Nb2O5、P2O5At least one of with clay.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248033A (en) * | 2005-04-25 | 2008-08-20 | 阿肯马法国公司 | Method for producing acrylic acid from glycerol |
| CN101563311A (en) * | 2006-12-19 | 2009-10-21 | 阿肯马法国公司 | Method for preparing acrylic acid from glycerol |
| CN101796012A (en) * | 2007-09-06 | 2010-08-04 | 阿肯马法国公司 | The method that is used for the reactive evaporation of glycerine |
| CN101801902A (en) * | 2007-09-20 | 2010-08-11 | 阿肯马法国公司 | Process for manufacturing acrolein from glycerol |
| CN102482187A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN102482189A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN103328428A (en) * | 2011-01-28 | 2013-09-25 | 阿肯马法国公司 | Improved process for manufacturing acrolein/acrylic acid |
-
2017
- 2017-07-28 CN CN201710628240.XA patent/CN109304162B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101248033A (en) * | 2005-04-25 | 2008-08-20 | 阿肯马法国公司 | Method for producing acrylic acid from glycerol |
| CN101563311A (en) * | 2006-12-19 | 2009-10-21 | 阿肯马法国公司 | Method for preparing acrylic acid from glycerol |
| CN101796012A (en) * | 2007-09-06 | 2010-08-04 | 阿肯马法国公司 | The method that is used for the reactive evaporation of glycerine |
| CN101801902A (en) * | 2007-09-20 | 2010-08-11 | 阿肯马法国公司 | Process for manufacturing acrolein from glycerol |
| CN102482187A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN102482189A (en) * | 2009-07-22 | 2012-05-30 | 阿肯马法国公司 | Method for producing bioresourced acrylic acid from glycerol |
| CN103328428A (en) * | 2011-01-28 | 2013-09-25 | 阿肯马法国公司 | Improved process for manufacturing acrolein/acrylic acid |
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