CN105749944A - Catalyst for preparing alpha-methacrylic acid from 2-methylacrolein with gas-phase catalytic oxidation method - Google Patents
Catalyst for preparing alpha-methacrylic acid from 2-methylacrolein with gas-phase catalytic oxidation method Download PDFInfo
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- CN105749944A CN105749944A CN201610169366.0A CN201610169366A CN105749944A CN 105749944 A CN105749944 A CN 105749944A CN 201610169366 A CN201610169366 A CN 201610169366A CN 105749944 A CN105749944 A CN 105749944A
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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
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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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
-
- 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
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
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- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention provides a catalyst for preparing alpha-methacrylic acid from 2-methylacrolein with a gas-phase catalytic oxidation method. The catalyst is characterized in that at least one of Te, As, Fe, Ni, Si, Nb, Zr and Ce is introduced to an existing molybdenum-phosphorus system catalyst formula, and the general formula of the catalyst is Mo(a)P(b)V(c)Cu(d)Sb(e)(Cs or/and K)(f)X(g)O(h), wherein X in the formula is selected from at least one of Te, As, Fe, Ni, Si, Nb, Zr and Ce; the subscripts a, b, c, d, e, f, g and h in the formula represent the atomic ratio of the elements; when a is equal to 12, b is larger than or equal to 0.1 and smaller than or equal to 3, c is larger than or equal to 0.01 and smaller than or equal to 3, d is larger than or equal to 0.01 and smaller than and equal to 3, e is larger than or equal to 0.01 and smaller than and equal to 2, f is larger than or equal to 0.01 and smaller than or equal to 4, g is larger than or equal to 0.01 and smaller than or equal to 3, and h is the sum of necessary oxygen atoms to meet the valence of the elements; when Cs and K exist simultaneously, the proportion of the relative amount is arbitrary. The catalyst remarkably increases the conversion rate of methylacrolein and the selectivity of a target product, and has long service life.
Description
One, technical field
The present invention relates to a kind of catalyst, be exactly a kind of catalyst being prepared α-methacrylic acid by methacrolein catalytic gas phase oxidation method.
Two, technical background
Relevant methacrolein (under be called for short methylacrolein) catalytic gas phase oxidation method produces α-methacrylic acid (under be called for short methacrylic acid) and achieved industrialization before more than 20 years, and has many improving.But, compared with producing acrylic acid with catalytic gas phase oxidation of acrolein method, it being used for the molybdenum phosphorus System Catalyst ratio producing methacrylic acid for producing acrylic acid molybdenum vanadium System Catalyst, activity and selectivity is all relatively low, and the life-span is short.
Prepare the catalyst of methacrylic acid both at home and abroad for methylacrolein catalytic gas phase oxidation method, great majority are all with phosphorus, molybdenum for Main Ingredients and Appearance, and have the structure of heteropoly acid and/or its salt.The shape of catalyst is generally granule, hollow lamellar, hollow annular and hollow cylinder, or by wrapped for the active ingredient of catalyst on inertia porous ball carrier.
Carry out in the oxidation reaction that methylacrolein catalytic gas phase oxidation prepares methacrylic acid using this kind of catalyst, usually at low relative humidity retrofilling catalyst and startup reactor, adopt lower temperature and relatively low-speed operation, and regularly catalyst is carried out reactivation, to maintain longer service life.Therefore, continue to improve the activity of catalyst, selectivity and catalyst and remain the current key improving methacrylic acid production technology level service life.
Three, summary of the invention
The present invention is directed to the defect existing for existing catalyst, it is desirable to provide a kind of catalysis activity is strong, selectivity is good and the catalyst of long service life, and existing molybdenum-phosphorus series catalysts is improved by be solved technical problem is that.
Catalyst alleged by the present invention is also molybdenum-phosphorus series catalysts, difference with the prior art is to introduce at least one and corresponding Elements Atom ratio thereof in the elements such as tellurium (Te), arsenic (As), ferrum (Fe), nickel (Ni), silicon (Si), niobium (Nb), zirconium (Zr) or cerium (Ce) in existing molybdenum-phosphorus series catalysts formula, and specifically this catalyst has below general formula:
Mo(a)P(b)V(c)Cu(d)Sb(e)(Cs or/and K)(f)X(g)O((h)
The X at least one element in the elements such as Te, As, Fe, Ni, Si, Nb, Zr or Ce in formula.
Subscript a, b, c, d, e, f, g, h represent the atomic ratio of each element, as a=12, and 0.1≤b≤3,0.01≤c≤3,0.01≤d≤3,0.01≤e≤2,0.01≤f≤4,0.01≤g≤3, h meets the oxygen atomicity sum that above-mentioned each Elements Atom valency is required.When there being Cs and k simultaneously, the ratio of its relative quantity is any.
Preferred Te and the As of X.
Prepare with phosphorus, molybdenum be main constituent composite oxides and the method for heteropoly acid and/or salt catalyst, adopt its sedimentation method more.Generally carrying out in the water at 80～120 DEG C, the response time, the water-soluble serous further evaporation of formation was solid at 3～20 hours, pulverized postforming, for hollow circular cylinder, ball etc..Heat treatment generally carries out 2～25 hours at 200～500 DEG C.This catalyst is also prepared by the sedimentation method.
Manufacture the raw material of catalyst, it is possible to combination uses the oxide of each element, ammonium salt, nitrate, acetate, carbonate etc..Such as, as molybdenum raw material, it is possible to use ammonium heptamolybdate, molybdic acid and molybdenum oxide；As phosphorus raw material, it is possible to use orthophosphoric acid, Metaphosphoric acid and pyrophosphoric acid etc.；The addition of potassium and caesium can use nitrate, carbonate or its hydroxide.Other elements are as the same.
Catalyst in the present invention can not load on carrier, it is also possible to add part fine-powdered inert carrier mixing use.These carriers mostly are sial and the silicon carbon compound of high-temperature process.
When carrying out methylacrolein gas phase catalytic oxidation reaction, employing is calandria type fixed bed reactor, and tube inner diameter is 20～30mm, pipe range 2800～3600mm, and catalyst is segmented into some sections in reaction casing pack, is at least two sections.Catalyst can dilute by inert ball if desired, and the inert ball of dilution part also counts the volume of catalyst.
Reaction generally carries out at ambient pressure, and reaction temperature is between 230～400 DEG C, it is particularly preferred between 260～340 DEG C.
Participate in the metering system aldehyde concentration in the unstrpped gas of reaction preferably within the scope of 4～6 moles of %；Oxygen concentration is within the scope of 5～15 moles of %, and the source of oxygen is usually the residual oxygen of previous step reaction and supplementary air；In unstripped gas, the concentration of water vapour is very important, and the mol ratio between it and methylacrolein is preferably in 1.5～1.8 scopes.Within the scope of this, be conducive to improving the selectivity of methacrylic acid, slow down the deterioration of catalyst so that reaction safely and smoothly carries out.What in unstripped gas, content was maximum is nitrogen, also has part oxycarbide and a small amount of rudimentary saturated aldehyde, ketone etc., and reaction is not had the impact of essence by them.
Unstrpped gas is very important at the space flow speed of catalyst " bed ", generally at 600～800h-1In scope, lower than this scope, the hot-spot (focus) that exothermic reaction produces can not stable operation owing to rate of heat dissipation is low；Air speed is excessive, can accelerate the degradation speed of catalyst, because this type of catalyst is substantially DNAcarrier free.
The methylacrolein being used as raw material in the present invention can by making isobutene. or tert-butyl alcohol catalytic gas phase oxidation provide with the catalyst of Mo Bi Fe Co system.That is, methacrylic acid isobutene. or the tert-butyl alcohol two step cascade reaction realize, namely the reaction product gas of first step generation methylacrolein is not separated, is made directly second step reaction, it is also possible to carry out second step reaction by the methylacrolein after separating as raw material.
This catalyst is simultaneously introduced As and Te, not only significantly improves the conversion ratio of methylacrolein catalytic gas phase oxidation process and the selectivity of target product, and methacrylic acid productivity declines very slow in course of reaction.Also the service life of catalyst is extended.
Methylacrolein conversion ratio and the definition of methacrylic acid yield are as follows:
Wherein A is the molal quantity of methylacrolein in unstripped gas, and B is the molal quantity of the methylacrolein reacted, and C is the molal quantity of the methacrylic acid generated.
Four, detailed description of the invention
The present invention is described in detail by the examples below, but the present invention is not limited to these examples.
Embodiment 1
Adding 810 grams of molybdenum trioxides, 30.70 grams of vanadium pentoxides, the phosphoric acid of 73.5 gram 85%, 3 grams of copper oxides, the arsenic acid of 46 gram 60% and 11 grams of telluric acids in 3.5 liters of pure water, at 100～110 DEG C, agitating heating refluxes 8 hours；Adding the solution having dissolved 30 grams of copper nitrates, 92 grams of cesium nitrates and 4.10 grams of antimony trioxides in 800 milliliters of water, heated and stirred continues to reflux 3 hours at 100～110 DEG C.Then concentration is evaporated, and adds 120 grams of ceramic fibres, be extruded into the hollow cylinder granule of ф 5 × 5 after being sufficiently mixed after being ground into fine powder.Dried in atmosphere in 390 DEG C of process 6 hours.
The composition of catalyst atomic ratio in addition to oxygen is
Mo12P1。2Cu0.3V0。6As0。35Te0。1Sb0。05Cs1
Internal diameter is the stainless steel tube 15 of 30mm, long 3200mm, and reaction gas outlet section fills 1350ml catalyst, fills the inert ball (ф 5) of 570ml catalyst and the 200ml being mixed with in feed(raw material)inlet section.Be at 285 DEG C at the temperature of molten salt adding thermal medium, pass into by 5% the methylacrolein of (volume, lower with), the oxygen of 10%, the water vapour of 9% and 76% the unstripped gas of nitrogen composition, space velocity is 800h-1, reaction carries out with normal pressure flow type.
Product is analyzed after carrying out 6 hours by reaction, and methylacrolein conversion ratio is 87.3% (mole), and methacrylic acid yield is 74.3% (mole).
Then successive reaction 3000 hours under these conditions, that product is analyzed as a result, methylacrolein conversion ratio is 87% (mole), the yield of methacrylic acid is 74.1% (mole).Catalyst runs 3000 hours under the reaction conditions almost without what change.
Embodiment 2
In the formula of embodiment 1, being added without telluric acid, 60% arsenic acid is changed to 66 grams, the preparation condition of catalyst, and the implementation condition of oxidation reaction is all with embodiment 1.
Reaction product is analyzed after carrying out 6 hours by reaction, and methylacrolein conversion ratio is 85.2% (mole), and the yield of methacrylic acid is 71.6% (mole).
Then carrying out successive reaction under these conditions 3000 hours, the analysis result of reactant is methylacrolein conversion ratio is 82.5% (mole), and the yield of methacrylic acid is 68.4% (mole).Catalyst performance declines substantially.
Embodiment 3
Replacing arsenic with telluro completely in the formula of embodiment 1, the consumption of telluric acid is 21 grams, and other is identical with embodiment 1.The gas phase catalytic oxidation reaction of methylacrolein is with embodiment 1.
Reaction product is analyzed after carrying out 6 hours by reaction, and methylacrolein conversion ratio is 83.8% (mole), and methacrylic acid yield is 70.6% (mole).
Then carrying out successive reaction under these conditions 3000 hours, the analysis result of reaction product is methylacrolein conversion ratio is 83.3% (mole), and methacrylic acid yield is 70.2% (mole).Catalyst performance is not decreased obviously.
Embodiment 4
Catalyst and catalyst placement method in the reactor is with embodiment 1
Oxidation reaction adopts two step tandems, and the reaction gas of the first step is not separated is directly entered the embodiment of the present invention 1 reactor.First step reaction uses Mo W Co Bi Fe Cs K Si O catalyst, and reaction tube is internal diameter 25mm, the stainless steel tube of long 3400mm 15, and it is 1500ml that catalyst fills volume；The process conditions of first step reaction are that to add the temperature of molten salt of thermal medium be 335 DEG C, and space velocity is 1150h-1, wherein isobutylene concentration be 5% (mole, lower with), oxygen concentration 12%, water vapor concentration is 8%, and all the other are nitrogen.First step reaction generation gas is cooled to 230 DEG C and is directly entered second step reactor.The thermal medium temperature of molten salt that adds of second step reaction is 285 DEG C.If necessary, second step reaction can supplement certain air, to ensure that second step reflects residue oxygen in implication and is not less than 2% (volume).Reaction still carries out with normal pressure flow type.
Product is analyzed after carrying out 6 hours by cascade reaction, and the conversion ratio of isobutene. is 99.2% (mole), and methylacrolein yield is 82.3% (mole), and methacrylic acid yield is 73.8% (mole).
Above-mentioned condition successive reaction 3000 hours, the result that cascade reaction product is analyzed is, the conversion ratio of isobutene. is 98.8% (mole), and methylacrolein yield is 84.2% (mole), and methacrylic acid yield is 73.5% (mole).Catalyst does not demonstrate obvious deterioration.
Claims (2)
1. the catalyst being prepared α-methacrylic acid by methacrolein catalytic gas phase oxidation method, it it is molybdenum-phosphorus series catalysts, base is characterised by: introducing at least one element in Te, As, Fe, Ni, Si, Nb, Zr or Ce element in existing molybdenum-phosphorus series catalysts formula, formula is as follows:
Mo(a)P(b)V(c)Cu(d)Sb(e)(Cs or/and K)(f)X(g)O(h)；
The X at least one element in Te, As, Fe, Ni, Si, Nb, Zr or Ce element in formula；
Subscript a in formula, b, c, d, e, f, g, h represent the atomic ratio of each element, as a=12, and 0.1≤b≤3,0.01≤c≤3,0.01≤d≤3,0.01≤e≤2,0.01≤f≤4,00.1≤g≤3, h meets the oxygen atomicity sum that above-mentioned each Elements Atom valency is required；When there being Cs and K simultaneously, the ratio of its relative quantity is any.
2. catalyst according to claim 1, it is characterised in that: in existing molybdenum-phosphorus series catalysts formula, introduce Te and As.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111050906A (en) * | 2017-10-20 | 2020-04-21 | 三菱化学株式会社 | α -method for producing catalyst for unsaturated carboxylic acid production, α -method for producing unsaturated carboxylic acid, and α -method for producing unsaturated carboxylic acid ester |
| CN114160201A (en) * | 2021-12-27 | 2022-03-11 | 中建安装集团有限公司 | Heteropolyacid catalyst and application thereof |
| CN114425381A (en) * | 2020-09-24 | 2022-05-03 | 中国石油化工股份有限公司 | Gas phase oxidation catalyst, preparation method and method for producing o-phthalaldehyde |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111050906A (en) * | 2017-10-20 | 2020-04-21 | 三菱化学株式会社 | α -method for producing catalyst for unsaturated carboxylic acid production, α -method for producing unsaturated carboxylic acid, and α -method for producing unsaturated carboxylic acid ester |
| CN114425381A (en) * | 2020-09-24 | 2022-05-03 | 中国石油化工股份有限公司 | Gas phase oxidation catalyst, preparation method and method for producing o-phthalaldehyde |
| CN114425381B (en) * | 2020-09-24 | 2023-10-13 | 中国石油化工股份有限公司 | Gas-phase oxidation catalyst, preparation method and method for producing phthalic dicarboxaldehyde |
| CN114160201A (en) * | 2021-12-27 | 2022-03-11 | 中建安装集团有限公司 | Heteropolyacid catalyst and application thereof |
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