CN101219947A - Method for gas-phase catalytic oxidation using a fixed bed reactor - Google Patents
Method for gas-phase catalytic oxidation using a fixed bed reactor Download PDFInfo
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- CN101219947A CN101219947A CNA2007101441995A CN200710144199A CN101219947A CN 101219947 A CN101219947 A CN 101219947A CN A2007101441995 A CNA2007101441995 A CN A2007101441995A CN 200710144199 A CN200710144199 A CN 200710144199A CN 101219947 A CN101219947 A CN 101219947A
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Abstract
The invention provides a method of gas-phase catalytic oxidation, in particular, a production method of (meth)acrylic acid, which enables stable continuous operation of gas-phase catalytic oxidation over a long term, maintaining high yield and suppressing increase in pressure loss. In the method a fixed bed reactor is used, in which a treating agent for removing organic substance and/or carbides, preferably a treating agent having an adsorption capacity of at least 0.05% by mass, as measured by crotonaldehyde as an indicator of organic substance, is disposed on the upstream side of the gas-phase oxidation catalyst layer in respect of the direction of the gas flow. It is desirable that at least a part of the treating agent is exchanged at a frequency of at least once a year.
Description
Technical field
The present invention relates to improving one's methods of a kind of catalytic gas phase oxidation that uses fixed-bed reactor.
Background technology
In the petrochemical industry field, use the gas phase catalytic oxidation reaction of fixed-bed reactor frequently to be used.Yet the initial feed that is used for these gas phase catalytic oxidation reactions needn't have high purity.
For example, in the production of acrylic or methacrylic acid (after this general designation is made " (methyl) vinylformic acid "), in fs catalytic gas phase oxidation step, at first hydrocarbon is changed into undersaturated aldehyde, in subordinate phase catalytic gas phase oxidation step, undersaturated aldehyde is changed into (methyl) vinylformic acid then.In these reactions, usually undersaturated aldehyde is separated and purifying between during the course, but the reactant gases that produces in the fs catalytic gas phase oxidation step is introduced in the subordinate phase catalytic gas phase oxidation step, as it is or when necessary information after adding molecular oxygen, thereby (methyl) vinylformic acid is provided.Therefore, since organism that the impurity that reaction contains in the initial feed produces or carbide (after this these general designations are made " catalyst-initiator ") on fs catalytic gas phase oxidation catalyzer (" fs catalyzer ") deposition and gather, perhaps because the deposition on the catalytic gas phase oxidation catalyzer (" subordinate phase catalyzer ") of catalyst-initiator in subordinate phase of the generations such as byproduct that fs reaction forms and gathering, when these catalyzer use one section fixed during the cycle in reaction continuously, will produce such problem, for example, the yield of the target product that causes owing to the pressure-losses increase of catalyst performance decline and catalyst layer descends in time.
The method that is used to address this is that, for example, JP Hei 6 (1994)-262081A and JP Hei 6 (1994)-263689A are (corresponding to United States Patent (USP) 5,442,108) disclose by regularly handling, for example, the combustion catalysis agent inhibitor makes the method for catalyst regeneration.More particularly, the prior art reference paper discloses safety and has made the method for catalyst regeneration effectively, this method comprises, regularly stopped reaction and when making catalyzer remain on filling state in the pipe reactor heat treatment catalyst, make the gas phase miscellany that contains molecular oxygen and steam pass through reacting pipe simultaneously.These methods have the advantage that can make catalyst regeneration, and it need not be taken out from reacting pipe.But because the thermal load that during pyroprocessing catalyzer is applied, life of catalyst may shorten owing to each manipulation of regeneration, and this depends on the kind of catalyzer.The method that causes catalyst life to shorten may be not satisfied solution economically, therefore need can be in longer cycle the steady and continuous method of operating.
Summary of the invention
In view of the above, the method that the purpose of this invention is to provide a kind of catalytic gas phase oxidation, especially, by catalytic gas phase oxidation production (methyl) acrylic acid, it can steady and continuous operation in the long cycle, keeps high yield level simultaneously and suppresses the increase of the pressure-losses.
We have been engaged in the further investigation of finishing above-mentioned target, and find: using one or more fixed-bed reactor to implement in the catalytic gas phase oxidation with the reacting pipe that has loaded gas-phase oxidation catalyst, be positioned over the upstream side of catalyst layer when the treatment agent of the catalyst-initiator that will be used for removing reactant gases, treatment agent preferably has the loading capacity of at least 0.05 quality %, as measuring as organic indicator by crotonaldehyde, preferably change at least a portion treatment agent termly, then can stop the catalyzer decline, and steady and continuous operation in the long cycle, the pressure-losses increase that keeps high yield simultaneously and the suppress catalyst layer possibility that becomes.
Thereby, according to the present invention, a kind of method of catalytic gas phase oxidation is provided, operate continuously catalytic gas phase oxidation wherein, method is characterised in that the use fixed-bed reactor, the treatment agent that wherein is used for removing the catalyst-initiator of reactant gases is placed on the upstream side of gas-phase oxidation catalyst layer with respect to gas flow direction, preferably, treatment agent has the loading capacity of at least 0.05 quality %, as measuring as organic indicator by crotonaldehyde, and preferably, change at least a portion treatment agent with annual at least frequency.In catalytic gas phase oxidation method of the present invention, preferably, be placed on treatment agent in one or more reacting pipes and/or in the space in the reactor, for example, be placed on the top (upper part) of supporting pipeline upper board (tube-holdingupper plate) in the reactor.
Removing the catalyst-initiator of indication here means effectively organism or the carbide absorption that will form, absorbs or is deposited on the treatment agent, so that it is removed from reactant gases, and any contact the between blocking-up catalyst-initiator and catalyzer, the organism of described formation or carbide are attributable to the byproduct that forms in impurity contained in the reaction initial feed or the fs reaction.
In catalytic gas phase oxidation method of the present invention, preferably, as at least a portion treatment agent, this can make production cost reduce with the regenerated treatment agent.
The present invention is used for producing (methyl) vinylformic acid by initial feed such as propylene, iso-butylene, tertiary butyl alcohol, methyl tertiary butyl ether etc. with the two stage catalytic gas phase oxidations of molecular oxygen in the presence of catalyzer aptly.Especially, described method optimum ground is used to use the two stages oxidation of passing through propylene of polyphone type reactor to produce vinylformic acid.
Catalytic gas phase oxidation method of the present invention can suppress catalyst-initiator and deposit on the catalyzer, and make it possible in the long cycle, implement stable catalytic gas phase oxidation continuously and catalyst themselves can not fail, keep high yield and suppress the increase of the pressure-losses of catalyst layer.Therefore, according to production method of the present invention, can expect that (methyl) acrylic acid production cost greatly reduces.
Embodiment
Catalytic gas phase oxidation method of the present invention comprises the use of fixed-bed reactor, and the placement that is used to remove the treatment agent of catalyst-initiator, described fixed-bed reactor have one or more reacting pipes of loading gas-phase oxidation catalyst (after this can simply be called " catalyzer "), described treatment agent is placed in the gas flow path of the compound that contains initial feed and/or generated (after this placement location can simply be called " in reactor "), preferably, treatment agent has the loading capacity of at least 0.05 quality %, as measuring as organic indicator by crotonaldehyde, preferably, change at least a portion treatment agent with annual at least frequency.
Here " fixed-bed reactor " are meant such equipment, wherein the gas-phase oxidation catalyst in its reacting pipe of packing into statically in the presence of, the initial gas of the gas inlet charging by reacting pipe carries out catalytic gas phase oxidation, and the gas that contains the finished product is discharged by the pneumatic outlet of reacting pipe.Described equipment can be that independent equipment maybe can be the equipment that is attached in the production equipment.
Can be used for fixed-bed reactor of the present invention and have the structure substantially the same with the fixed-bed reactor that are generally used for catalytic gas phase oxidation, the treatment agent that just will be used for removing catalyst-initiator is placed on reactor, does not have special restriction in addition.Therefore, fixed-bed reactor of the present invention can be, for example, the shell-tube type reactor, the catalyzer of wherein in the reacting pipe of many minor diameters, packing into, perhaps isolated reactor is in the single large diameter reacting pipe of wherein catalyzer being packed into.
According to the present invention, changed the primary treatment agent, more preferably at least one year twice in preferred at least one year.Use treatment agent continuously and when not changing, removing of catalyst-initiator becomes not thorough, and catalyst-initiator is deposited on the catalyst layer when long-term, cause the disadvantageous effect of the increase of the reduction of catalyst activity or the pressure-losses.Changing the quantity of the treatment agent that will change each time can suitably select according to the condition of use, can removable parts or the treatment agent of all amts.
Means for changing can adopt any known replacing method.For example, can use the top sucking-off treatment agent of suction tube from reacting pipe, described in JP 2002-301355A or international open WO 98/02239, can the sucking-off treatment agent when gas under pressure is introduced reacting pipe.When changing treatment agent, can use novel agent or recovery catalyst.
Here " recovery catalyst " is meant once used treatment agent, and wherein after taking out from reacting pipe, the catalyst-initiator that the mode by thermal treatment or washing will deposit is thereon removed.The condition of thermal treatment or washing does not have special restriction, and it can suitably be determined according to the deposition quantity of catalyst-initiator.
For heat treated condition, should select for example atmosphere, temperature and time, these conditions can make the catalyst-initiator that will be deposited on the treatment agent by burning remove and can not make treatment agent to degenerate.Usually the condition that is enough to implement was assigned 2-72 hour at 300-700 ℃ under the atmosphere of the gas that contains molecular oxygen, preferably assigned 3-24 hour at 350-600 ℃.
Can implement washing can being deposited on that catalyst-initiator on the treatment agent is removed under the condition that treatment agent is degenerated.Can implement to use for example washing of acid, alkaline aqueous solution or organic solvent.When implementing heating simultaneously, can improve washing effect.
Remove as long as impurity that can be contained in the initial feed by reaction or fs are reacted organism or the carbide that formed byproduct produces, just do not have special restriction being used for treatment agent of the present invention.The example of useful treatment agent comprises oxide compound, composite oxides or carbonate (after this general designation is made " (compound) oxide compound etc. "), and it contains at least a following element or its mixture of being selected from: aluminium (Al), silicon (Si), titanium (Ti), zirconium (Zr), zinc (Zn), magnesium (Mg), calcium (Ca) and niobium (Nb).As concrete example, can enumerate aluminum oxide, silicon oxide, titanium oxide, zirconium white, silica-alumina, silicon oxide-titanium oxide, silicon oxide-zinc oxide, silicon oxide-zirconium white, aluminium oxide-titanium oxide, aluminum oxide-zinc oxide, aluminium oxide-zirconium oxide, oxidation titania-zirconia, zinc oxide-zirconium white, zeolite, magnesiumcarbonate, lime carbonate etc.In these treatment agents, contain at least a oxide compound or the composite oxides that are selected from the element of aluminium, silicon, titanium and zirconium, particularly, the composite oxides that contain aluminium and silicon are preferred.
The treatment agent that can prepare the composite oxides that contain aluminium and silicon, for example, the mixture forming that makes alumina powder and colloidal silica is the shape of expection and calcines it.In this case, in the total amount of per 100 mass parts (by oxide compound) alumina powder and colloidal silica, the quantity of alumina powder is the 30-97 mass parts, and preferred 40-95 mass parts especially is the 50-90 mass parts; The quantity of colloidal silica is the 3-70 mass parts, and preferred 5-60 mass parts especially is no more than 50 mass parts.Preferred calcining temperature is 500 ℃-1300 ℃, more preferably 600 ℃-1200 ℃, and especially 700 ℃-1100 ℃.Preferred calcination time is 0.5-50 hour, especially 1-20 hour.
Can also contain the treatment agent of the composite oxides of aluminium and silicon by the following manner preparation, for example, the mixture forming that makes alumina powder, alumina sol and colloidal silica is the shape of expection and calcines it.In this case, in the total amount of alumina powder, alumina sol and the colloidal silica of per 100 mass parts, alumina powder and alumina sol add up to the 60-97 mass parts, preferred 70-95 mass parts, especially, the 80-90 mass parts; The blended colloidal silica is the 3-40 mass parts, preferred 5-30 mass parts, especially 10-20 mass parts.
In addition, in the total amount of the alumina powder of per 100 mass parts and alumina sol, the mixing quantity of alumina powder is the 60-97 mass parts, is preferably the 70-96 mass parts, especially the 85-95 mass parts; The mixing quantity of alumina sol is the 3-40 mass parts, preferred 4-30 mass parts, especially 5-15 mass parts.
Preferred calcining temperature is 600 ℃-1300 ℃, more preferably 650 ℃-1200 ℃, and especially 700-1100 ℃.Preferred calcination time is 0.5-50 hour, particularly 1-20 hour.
Treatment agent can also adopt the form of the mixture that contains two or more above-mentioned (compound) oxide compounds etc., perhaps as load on the form of (compound) oxide compound on another kind (compound) oxide compound etc. etc., the form of perhaps above-mentioned (compound) oxide compound etc. and non-above-mentioned solid mixture, perhaps as load on the form of (compound) oxide compound on the non-above-mentioned solid etc.
Shape to treatment agent does not have special restriction, can select shape arbitrarily.For example, can enumerate those shapes, for example spherical, cylindric (column), cylindric (cylinder), starlike, ring-type, sheet, shape such as coccoid with common tabletting machine, extrusion shaping machine or tablets press moulding.If the size of treatment agent is too little,, it reacts thereby can making the pressure-losses increase and hinder effectively.On the contrary, if its size is too big, can cause the removal of non-sufficient catalyst-initiator.Therefore, its preferred mean diameter should be 1mm-15mm, more preferably 2mm-12mm, especially 3mm-10mm.As long as its size falls in the scope of above-mentioned mean diameter, can also use two or more treatment agents of different size, as be compressed into multilayer, perhaps can use a plurality of treatment agents of different size, as mixed.
Use crotonaldehyde can measure in the following way as the loading capacity of the treatment agent of organism indicator.Yet,, also can use similar method as long as can measure the actual loading capacity of treatment agent.With pack into the fixed bed mobile units of Controllable Temperature of the treatment agent of specified amount, and under flowing nitrogen or air, keep 350 ℃ temperature.With vapor pressure crotonaldehyde is gasified in bubbling equipment etc., or by controlled temperature or feeding rate, use vaporizer etc., the quantity of adjusting its steam and evaporation to be obtaining normality, and its upstream side from treatment agent is introduced.After feeding gaseous state crotonaldehyde specific time, take out treatment agent, at high temperature heat-treat.Handle the change of its quality of front and back or measure quality change by measurement, can determine organic absorption with thermal analyzer.
Can be according to kind, proportion and shape and kind, proportion and the shape of catalyzer and the rate of utilization that rate of utilization is suitably adjusted treatment agent of each treatment agent that uses, but without any special restriction.But, when rate of utilization is too low, may not can remove catalyst-initiator fully.Otherwise, when rate of utilization is too high, use the increase that can cause production cost more than treatment agent that must quantity.Therefore, the rate of utilization of treatment agent is by treatment agent, and treatment agent: catalyzer (volume ratio) is preferably 1: 0.5-100, more preferably 1: 2-50, especially 1: 3-30.
In the employed in the present invention fixed-bed reactor, it can be to be enough to suppress catalyst-initiator to be deposited on position on the used catalyzer that treatment agent is placed on position in the reactor, as long as treatment agent can be taken out and recharge individually, just there is not special restriction.Preferably, when placing it in position that gas temperature is lower than the catalyst layer temperature and promptly be lower than the position of temperature of reaction, the removal effect of catalyst-initiator will be strengthened.Therefore, the upside that treatment agent is placed on reacting pipe is advantageously, more particularly, treatment agent is placed on the top of catalyst layer in the reacting pipe or be placed on support in the reactor pipeline upper board above.
As the example of the catalytic gas phase oxidation to be performed according to the present invention, what can enumerate is the catalytic gas phase oxidation of being produced unsaturated aldehyde and/or unsaturated carboxylic acid by unsaturated hydrocarbons etc.; Close the catalytic gas phase oxidation of carboxylic acid by unsaturated aldehyde production insatiable hunger; Produce the catalytic gas phase oxidation of unsaturated nitrile by unsaturated hydrocarbons and ammonia; With the catalytic gas phase oxidation of producing unsaturated carboxylic acid by stable hydrocarbon.
In the operation of these catalytic gas phase oxidations, the present invention is advantageously used in by unsaturated hydrocarbons etc. and produces the catalytic gas phase oxidation of unsaturated carboxylic acid via unsaturated aldehyde, especially, is used for producing acrylic acid catalytic gas phase oxidation by propylene through propenal.For example, produce in the acrylic acid through propenal by propylene this, with regard to propylene oxidation catalyzer (" fs catalyzer "), the present invention is for suppressing it by the decline that catalyst-initiator caused that stems from the impurity that contains in the initial propylene, perhaps when circulating reaction gas, it is effective suppressing by the decline that catalyst-initiator caused that contains in the recycle gas.With regard to catalyst for oxidation of acrolein (" subordinate phase catalyzer "), its byproduct that forms in reacting for the inhibition fs also is effective to the disadvantageous effect of subordinate phase catalyzer.And then the present invention also is effective for acrylic acid production of using propane to make initial feed.
As long as it is to be generally used for this catalyst for reaction, the catalyzer that is used for this catalytic gas phase oxidation just there is not special restriction.Particularly, for example, for catalyzer, preferably by the composite oxide catalysts of following formula (1) expression by the fs catalytic gas phase oxidation of production of propylene propenal:
Mo
aW
bBi
cFe
dA
eB
fC
gD
hO
x (1)
Wherein, Mo is a molybdenum; W is a tungsten; Bi is a bismuth; Fe is an iron; A is at least a element that is selected from nickel and cobalt; B is the element that is selected from basic metal, alkaline-earth metal and thallium at least; C is the element that is selected from phosphorus, arsenic, boron and niobium at least; D is the element that is selected from silicon, aluminium and titanium at least; O is an oxygen; A, b, c, d, e, f, g, h and x represent Mo, W, Bi, Fe, A, B, C, the atomic ratio of D and O, it satisfies following inequality respectively, wherein 2≤a≤10,0≤b≤10 and a+b=12,0.1≤c≤10,0.1≤d≤10,1≤e≤20,0.005≤f≤3,0≤g≤4 and 0≤h≤15, x is the numerical value of determining according to the oxidation state of every kind of element.
Same for the catalyzer of producing acrylic acid subordinate phase catalytic gas phase oxidation by propenal, particularly preferably be composite oxide catalyst by following formula (2) expression:
Mo
mV
nQ
qR
rS
sT
tO
y (2)
Wherein, Mo is a molybdenum; V is a vanadium; Q is the element that is selected from tungsten and niobium at least; R is the element of chosen from Fe, copper, bismuth, chromium and antimony at least; S is the element that is selected from basic metal and alkaline-earth metal at least; T is the element that is selected from silicon, aluminium and titanium at least; With O be oxygen; And m, n, q, r, s, t and y represent Mo, V, Q, R, S, the atomic ratio of T and O, it satisfies following inequality respectively, m=12 wherein, 2≤n≤14,0≤q≤12,0≤r≤6,0≤s≤6,0≤t≤30, x is the numerical value of determining according to the oxidation state of every kind of element.
In production method of the present invention, vinylformic acid is the finished product that following method is produced, this method comprises that propylene makes the catalytic gas phase oxidation of initial feed and molecular oxygen, is used for main production and makes the propenal of midbody compound, and make propenal and molecular oxygen carry out catalytic gas phase oxidation subsequently.In this case, preferably use fixed-bed reactor, described fixed-bed reactor have loaded the catalytic gas phase oxidation that is used for by propylene and molecular oxygen produce propenal the fs catalyzer reacting pipe and loaded the reacting pipe that is used for producing acrylic acid subordinate phase catalyzer by the catalytic gas phase oxidation of propenal.In this fixed-bed reactor,, treatment agent can be placed on the upstream side of fs catalyzer or subordinate phase catalyzer with respect to gas flow direction.
Except treatment agent is placed in the reactor, for the reaction conditions of catalytic gas phase oxidation, in general, they can be with to be generally used for those of catalytic gas phase oxidation substantially the same, and do not have special restriction.For example, producing in propenal or the acrylic acid by the catalytic gas phase oxidation of propylene or propane, for example, gaseous mixture is contacted with catalyzer under following condition and react, temperature is 250 ℃-450 ℃, and preferred 260 ℃-400 ℃, pressure is normal atmosphere-1MPa, preferably be not higher than 0.8MPa, and air speed (STP) is 300h
-1-5000h
-1, preferred 500h
-1-4000h
-1, described gaseous mixture comprises precursor compound such as propylene or the propane of 1-15 volume %, preferred 4-12 volume %, the 1-10 volume doubly, preferred 1.5-8 volume precursor compound molecular oxygen doubly; With rare gas element (for example nitrogen, carbonic acid gas, steam etc.) as thinner.
According to the present invention, as the following examples proof, can under the situation that does not have the catalyzer decline, carry out gas phase catalytic oxidation reaction, keep high yield level and suppress the pressure-losses increasing, make it possible to steady and continuous operation in longer cycle thus.Therefore, according to production method of the present invention, can be effectively, stably obtain propenal or vinylformic acid with high yield.
Embodiment
Hereinafter reference work embodiment is more specifically explained the present invention, be understood that the present invention never is limited to embodiment certainly, but can implement, until the degree of the spirit that satisfies above and following explanation with any suitable correction.All this corrections are included within the technical scope of the present invention.
Catalytic performance
The vinylformic acid yield that limits by following equation comes assess performance:
Vinylformic acid yield (mol%)=(mole number of the acrylic acid mole number/charging propylene of formation) * 100.
The preparation of gas-phase oxidation catalyst I
The gas-phase oxidation catalyst that is used for testing, promptly, be used to produce the fs catalyzer of the catalytic gas phase oxidation of the propylene of propenal and molecular oxygen, with the used subordinate phase catalyzer of catalytic gas phase oxidation that is used to produce acrylic acid propenal and molecular oxygen, by preparing according to the method described in the embodiment 1 of JP Sho 64 (1989)-63543A.
Except carrier and oxygen, these catalyzer composed as follows described, press atomic ratio measuring:
The fs catalyzer:
Co
4Fe
1，Bi
1W
2Mo
10Si
1.35K
0.06
The subordinate phase catalyzer:
Mo
12V
4.6Cu
2.2Cr
0.6W
2.4
The mensuration of the pressure-losses of catalyst layer
In the present invention, the pressure-losses is measured in the following way: the bottom of reacting pipe is opened, and measuring stress under the condition that air passes through with the speed of 30L (liter)/minute (standard state) from the top of reacting pipe is measured the difference with original pressure.
Embodiment 1
At first, the methylcellulose gum as binding agent of the alumina powder of 75 mass parts median sizes, 5 μ m and 5 mass parts is packed into kneading machine and thorough mixing.Then with the aluminum oxide (Al of 8 mass parts median size 10nm
2O
3) colloidal silica (SiO of colloidal sol and 17 mass parts median size 10nm
2) add mixture, and then add the water and the mixing of sufficient amount.With the mixture extrusion moulding, 1000 ℃ down dry and calcined 2 hours, and obtain the cylindrical aluminium oxide-silicon oxide treatment agent (A) of mean outside diameter 7mm and length 7mm.
Prepare two steel reacting pipes, each pipeline all has the length of the internal diameter of 25mm and 3000mm and is equipped with and is used to make heat-transfer medium round-robin external jacket, with one of them filling fs catalyzer, filling length reaches 2450mm, and the empty space (empty space) (first reacting pipe) of 500mm is left in the bottom.Another reacting pipe pack into subordinate phase catalyzer and treatment agent (A).The subordinate phase catalyzer occupies the pipeline from the 2000mm of bottom, and treatment agent (A) occupies 500mm (second reacting pipe) on the subordinate phase catalyzer.The upper end of two reacting pipes is connected with the steel pipe of internal diameter 20mm and length 4000mm, and it can be with electric heater from indirect heating.
Terminal first reacting pipe of introducing carries out catalytic gas phase oxidation from its underpart as initial gas with the gaseous mixture of 5 volume % propylene, 10 volume % oxygen, 25 volume % steam and 60 volume % nitrogen, to the air speed of fs catalyzer be 2200h
-1In this case, the temperature of reaction in first reacting pipe (temperature of heat-transfer medium) is 325 ℃, and the temperature of reaction in second reacting pipe (temperature of heat-transfer medium) is 260 ℃, and pipe connecting remains on 170 ℃.
When changing treatment agent (A) a time when per 4000 hours, use above-mentioned conversion unit propylene catalytic gas phase oxidation continuous operation 9600 hours.At the end points place of 4000 hours, 8000 hours and 9600 hours operation, analyze the exit gas of second reacting pipe, measure and extracting treatment agent (A) pressure-losses of subordinate phase catalyst layer afterwards.4000 hours therein and 8000 hours over and done with time point places, after the pressure-losses of measuring the subordinate phase catalyst layer, recharge new treatment agent (A) and continuation reaction.
The result observes, and compares with the starting stage of reaction, and the pressure-losses of subordinate phase catalyst layer does not increase.Extract treatment agent (A) before each, acrylic acid yield is respectively 88.7%, 87.2% and 86.6%.
Embodiment 2
Except only changing the primary treatment agent after over and done with, operate the gas phase catalytic oxidation reaction of propylene in the mode identical with embodiment 1 at 8000 hours.After 8000 hours reaction, extract treatment agent and measure the pressure-losses of catalyst layer.The pressure-losses is compared starting stage increase 0.1kPa.In addition, this moment, the vinylformic acid yield was 85.6 moles of %.
Embodiment 3
Except not changing treatment agent, reach 9600 hours with the catalytic gas phase oxidation of the mode operate continuously propylene identical with embodiment 1.After through 9600 hours, extract treatment agent and measure the pressure-losses of catalyst layer.The pressure-losses is compared starting stage increase 2.1kPa.In addition, this moment, the vinylformic acid yield was 82.7 moles of %.
Embodiment 4-7
Except in test (run) each time, using the treatment agent of preparation in the following manner, repeat embodiment 1: use magnesiumcarbonate (embodiment 4), lime carbonate (embodiment 5) or zirconium white (embodiment 6) to substitute colloidal silica respectively, perhaps use titanium oxide (embodiment 7) instead of alumina.
As a result, in any case, all do not observe the pressure-losses increase of subordinate phase catalyst layer.
Embodiment 8
Catalytic gas phase oxidation with the mode operate continuously propylene identical with embodiment 1 reaches 4000 hours.After this extract treatment agent (A), by in air atmosphere, calcining 5 hours treatment agents of usefulness (A) of regenerating down in 500 ℃.Thereby the regenerated treatment agent (A) and the gas phase catalytic oxidation reaction of propylene is continued of recharging.After this operant response reaches 4000 hours, measures the pressure-losses of subordinate phase catalyst layer in the mode identical with embodiment 1.Observe than the starting stage, the pressure-losses does not increase.
The preparation of gas-phase oxidation catalyst II
Produce the employed fs catalyzer of propenal and produce the employed subordinate phase catalyzer of vinylformic acid by the catalytic gas phase oxidation of propylene and molecular oxygen according to the preparation of the method described in the embodiment 1 of JP Sho 64 (1989)-63543A by the catalytic gas phase oxidation of propenal and molecular oxygen.
Except carrier and oxygen, these catalyzer composed as follows described, press atomic ratio measuring:
The fs catalyzer:
Co
4Fe
1.1Bi
1.1W
1Mo
10Si
1K
0.07
The subordinate phase catalyzer:
Mo
12V
5Cu
2Cr
0.5W
2。
The preparation of treatment agent
Treatment agent (A)
With the starch as binding agent of the alumina powder of 70 mass parts median sizes, 15 μ m and 5 mass parts pack into kneading machine and thorough mixing.Then with the colloidal silica (SiO of 30 mass parts median size 50nm
2) add, and then add the water of sufficient amount, mix subsequently.With this mixture extrusion moulding, 800 ℃ down dry and calcined 2 hours, and obtain the cylindrical aluminium oxide-silicon oxide treatment agent (A) of mean outside diameter 7mm and length 7mm.
Treatment agent (B)-(D)
Except substituting colloidal silica with titanium oxide sol [treatment agent (B)] or zirconia sol [treatment agent (C)], or with titanium oxide [treatment agent (D)] instead of alumina, the preparation process of re-treatment agent (A) is to provide treatment agent (B), (C) and (D) respectively.
Treatment agent (E)
Except the quantity with alumina powder increases to 90 mass parts, with colloidal silica (SiO
2) quantity become 10 mass parts and calcining temperature be increased to 1000 ℃, with treatment agent (A) similarly mode prepare treatment agent (E).
Treatment agent (A2) and (A3)
Except respectively their size being made 9mm external diameter * 9mm length [treatment agent (A2)] and 5mm external diameter * 5mm length [treatment agent (A3)], with treatment agent (A) similarly mode prepare treatment agent (A2) and (A3).
The measurement of organism loading capacity
Take by weighing the 50g treatment agent, with its fixed bed mobile units and remain on 350 ℃ of packing into.After remaining on 10 ℃ crotonaldehyde bubbling, nitrogen fed from the upstream side of treatment agent with the speed of 170ml/min wherein reach 1 hour.After adsorption treatment, in up to 500 ℃ air with the treatment agent thermal treatment of all amts.Measure the quality change of thermal treatment front and back.
Determine organic loading capacity by following equation:
Organic loading capacity (quality %)=[weight reduces (g)/treatment agent (g)] * 100
Embodiment 9
Prepare two steel reacting pipes, each pipeline all has the length of the internal diameter of 25mm and 3000mm and is equipped with and is used to make heat-transfer medium round-robin external jacket, with one of them (first reacting pipe) filling fs catalyzer, be filled to the length of 2450mm from the inlet side (upper end) of reactant gases, on leave the space of 300mm.Another reacting pipe (second reacting pipe) loads treatment agent (A) and subordinate phase catalyzer, is filled to the length of 500mm and 2200mm respectively from reaction gas inlet side (upper end).Be connected the outlet (lower end) of first reacting pipe and the inlet (upper end) of second reacting pipe with the steel pipe of length 4000mm with internal diameter 20mm, described steel pipe can be used the electric heater indirect heating.
Then the gaseous mixture of the nitrogen of 5 volume % propylene, 10 volume % oxygen, 15 volume % steam and 70 volume % is introduced first reacting pipe as initial gas from inlet side and carries out catalytic gas phase oxidation, to the air speed (STP) of fs catalyzer be 1200h
-1In this case, the temperature of reaction in first reacting pipe (temperature of heat-transfer medium) is 325 ℃, and the temperature of reaction in second reacting pipe (temperature of heat-transfer medium) is 260 ℃, and pipe connecting remains on 170 ℃.
When changing treatment agent (A) a time when per 4000 hours, use above-mentioned conversion unit propylene catalytic gas phase oxidation continuous operation 9600 hours.At the end points place of 4000 hours, 8000 hours and 9600 hours operation, analyze the gas that leaves second reacting pipe outlet (lower end), after extracting treatment agent A, measure the pressure-losses of subordinate phase catalyst layer.After this new treatment agent (A) that recharges also continues reaction.The variation of the pressure-losses of vinylformic acid yield and subordinate phase catalyst layer is shown in the table 1.
Embodiment 10
Except through only changing the primary treatment agent after 8000 hours the operation, with the catalytic gas phase oxidation of the mode operate continuously propylene identical with embodiment 9.The variation of the pressure-losses of vinylformic acid yield and subordinate phase catalyst layer is shown in the table 1.
Embodiment 11
Except with loading capacity being Ceramic Balls (its loading capacity is measured as organic indicator by crotonaldehyde) the alternate process agent (A) of 0.01 quality %, with the catalytic gas phase oxidation of the mode operate continuously propylene identical with embodiment 9.Make reaction operate continuously 9600 hours, and after the operation of 4000 hours and 8000 hours, change Ceramic Balls.The variation of the pressure-losses of vinylformic acid yield and subordinate phase catalyst layer is shown in the table 1.
Embodiment 12
Except through only changing Ceramic Balls after 8000 hours the operation one time, with the catalytic gas phase oxidation of the mode operate continuously propylene identical with embodiment 11.The variation of the pressure-losses of vinylformic acid yield and subordinate phase catalyst layer is shown in the table 1.
Embodiment 13-16
Except using treatment agent (B) (embodiment 13), treatment agent (C) (embodiment 14), treatment agent (D) (embodiment 15) or treatment agent (E) (embodiment 16) alternate process agent respectively, repeat embodiment 9.The loading capacity of each treatment agent is measured as organic indicator by crotonaldehyde.The variation of the pressure-losses of vinylformic acid yield and subordinate phase catalyst layer is shown in the table 1.
Embodiment 17
Make the catalytic gas phase oxidation operate continuously 4000 hours of propylene in the mode identical with embodiment 9.After this extract treatment agent (A), by 500 ℃, in air atmosphere 5 hours calcination processing, exhausted treatment agent (A) is regenerated.Thereby, load regenerated treatment agent (A) again and continue reaction.The vinylformic acid yield in the current test and the pressure-losses of subordinate phase catalyst layer are shown in the table 1.
Embodiment 18
Except with two kinds of treatment agents, promptly at the treatment agent (A2) of the 250mm of upstream side with at the treatment agent (A3) of the 250mm in downstream side, the packing layer that forms substitutes the treatment agent (A) of second reacting pipe that occupies 500mm, with the catalytic gas phase oxidation of the mode operate continuously propylene identical with embodiment 9.The pressure-losses of vinylformic acid yield and subordinate phase catalyst layer is shown in the table 1.
Embodiment 19
Except the empty space in first reacting pipe being filled to the length of 200mm, operate the catalytic gas phase oxidation of propylene in the mode identical with embodiment 9 with treatment agent (A).The outlet of vinylformic acid collector at second reacting pipe connected, to capture vinylformic acid.The vinylformic acid collection rate is 95%.Comprise that with 50% the discharge gas that leaves collector of steam is circulated to the inlet of first reacting pipe.Add propylene and air to recycle gas to adjust the latter's concentration, make it contain the oxygen of the propylene of 5 volume %, 10 volume % and the steam of 15 volume %.All other operational condition is identical with embodiment 9.The variation of the pressure-losses of vinylformic acid yield and fs catalyst layer is shown in the table 1.
Table 1
| Treatment agent | The loading capacity of crotonaldehyde (quality %) | The pressure-losses of vinylformic acid yield and subordinate phase | After 4000 hours | After 8000 hours | After 9600 hours | ||
| Embodiment 9 | (A) | 0.28 | Vinylformic acid yield (%) | 87.7 | 86.2 | 85.9 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.1 | 3.1 | 2.9 | |||
| Extract after the treatment agent | 2.8 | 2.8 | 2.8 | ||||
| Embodiment 10 | (A) | 0.28 | Vinylformic acid yield (%) | 87.6 | 85.6 | 84.9 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | - | 4.4 | 3.0 | |||
| Extract after the treatment agent | - | 2.9 | 2.9 | ||||
| Embodiment 11 | Ceramic Balls | 0.01 | Vinylformic acid yield (%) | 86.7 | 85.3 | 84.4 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.6 | 4.6 | 5.3 | |||
| Extract after the treatment agent | 3.3 | 4.4 | 5.2 | ||||
| Embodiment 12 | Ceramic Balls | 0.01 | Vinylformic acid yield (%) | 86.7 | 83.7 | 83.0 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | - | 4.8 | 5.4 | |||
| Extract after the treatment agent | - | 4.6 | 5.2 | ||||
| Embodiment 13 | (B) | 0.22 | Vinylformic acid yield (%) | 87.6 | 86.1 | 85.8 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.2 | 3.2 | 3.0 | |||
| Extract after the treatment agent | 2.8 | 2.8 | 2.8 | ||||
| Embodiment 14 | (C) | 0.18 | Vinylformic acid yield (%) | 87.5 | 86 | 85.2 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.2 | 3.2 | 3.0 | |||
| Extract after the treatment agent | 2.8 | 2.8 | 2.8 | ||||
| Embodiment 15 | (D) | 0.33 | Vinylformic acid yield (%) | 87.8 | 86.4 | 86.0 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.2 | 3.2 | 3.0 | |||
| Extract after the treatment agent | 2.8 | 2.8 | 2.8 | ||||
| Embodiment 16 | (E) | 0.05 | Vinylformic acid yield (%) | 87.2 | 85.7 | 85.1 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.3 | 3.3 | 3.0 | |||
| Extract after the treatment agent | 2.8 | 2.9 | 2.9 | ||||
| Embodiment 17 | (A) regenerated | 0.28 | Vinylformic acid yield (%) | 87.6 | 86.3 | 85.8 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.1 | 3.1 | 2.9 | |||
| Extract after the treatment agent | 2.8 | 2.8 | 2.8 | ||||
| Embodiment 18 | (A2) (A3) laminated | 0.28 | Vinylformic acid yield (%) | 87.7 | 86.2 | 85.7 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.1 | 3.1 | 2.9 | |||
| Extract after the treatment agent | 2.8 | 2.8 | 2.8 | ||||
| Embodiment 19 | (A) | 0.28 | Vinylformic acid yield (%) | 87.9 | 86.5 | 86.1 | |
| The pressure-losses of subordinate phase (KPa) | Extract before the treatment agent | 3.2 | 3.2 | 3.1 | |||
| Extract after the treatment agent | 3.1 | 3.1 | 3.1 | ||||
Industrial applicibility
In catalytic gas phase oxidation according to the present invention, when keeping high yield level and suppressing pressure-losses increase, the decline of catalyzer has obtained significant inhibition, thereby can steady and continuous operation in longer cycle.In addition, needn't change expensive catalysts.Therefore, according to method of the present invention, can reduce significantly by main chemical such as the acrylic acid production cost that catalytic gas phase oxidation obtains.
Comparative Examples 1
Except not using treatment agent, reach 8000 hours with the gas phase catalytic oxidation reaction of the mode operate continuously propylene identical with embodiment 9.The pressure-losses of vinylformic acid yield and subordinate phase catalyst layer is shown in the table 2.
The decline of vinylformic acid yield and the increase of the pressure-losses are very significant, have therefore abandoned proceeding further reaction.
Table 2
| Treatment agent | The loading capacity of crotonaldehyde (quality %) | Vinylformic acid yield and in the pressure-losses of subordinate phase | After 8000 hours | |
| Comparative Examples 1 | No | - | Vinylformic acid yield (%) | 82.4 |
| The pressure-losses of subordinate phase (KPa) | 6.4 |
Claims (7)
1. a catalytic gas phase oxidation method is characterized in that, in implementing catalytic gas phase oxidation, use fixed-bed reactor, wherein will be used to remove the treatment agent of organism and/or carbide,, be positioned over the upstream side of gas-phase oxidation catalyst layer with respect to gas flow direction.
2. the process of claim 1 wherein that the loading capacity of treatment agent is at least 0.05 quality %, as measuring as organic indicator by crotonaldehyde.
3. claim 1 or 2 method wherein are positioned over treatment agent in one or more reacting pipes and/or in the space in the reactor, and the position is the upstream side with respect to the catalyst layer of gas flow direction.
4. each method among the claim 1-3 is wherein changed at least a portion treatment agent with annual at least frequency.
5. each method among the claim 1-4, wherein at least a portion treatment agent is the treatment agent that has been reproduced.
6. each method among the claim 1-5, wherein gas phase catalytic oxidation reaction is the acrylic acid reaction of two elementary reaction productions (methyl) by propylene, iso-butylene, the trimethyl carbinol or methyl-tert butanols.
7. the production acrylic acid of claim 6, it uses fixed-bed reactor, and wherein with respect to gas flow direction, treatment agent is placed on the downstream side of fs catalyst for reaction and the upstream side of subordinate phase catalyst for reaction.
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| JP2006198722A JP2008024644A (en) | 2006-07-20 | 2006-07-20 | Fixed bed reaction apparatus and use thereof |
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| JP2006198722 | 2006-07-20 | ||
| JP2007060460 | 2007-03-09 | ||
| JP2007060460A JP5311751B2 (en) | 2007-03-09 | 2007-03-09 | Fixed bed reactor and method of use thereof |
| JP2007-060460 | 2007-03-09 |
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| WO2015166911A1 (en) | 2014-04-30 | 2015-11-05 | 三菱レイヨン株式会社 | Method for producing (meth)acrylic acid |
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