CN1819869A - Oxidation process and reactor with modified feed system - Google Patents

Oxidation process and reactor with modified feed system Download PDF

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Publication number
CN1819869A
CN1819869A CN03826973.2A CN03826973A CN1819869A CN 1819869 A CN1819869 A CN 1819869A CN 03826973 A CN03826973 A CN 03826973A CN 1819869 A CN1819869 A CN 1819869A
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CN
China
Prior art keywords
reactor
reactor tube
feed
gas mixture
bed
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Pending
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CN03826973.2A
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Chinese (zh)
Inventor
O·S·弗吕谢
B·R·凯斯
C·D·墨菲
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Publication of CN1819869A publication Critical patent/CN1819869A/en
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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
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
    • B01J8/0085—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction promoting uninterrupted fluid flow, e.g. by filtering out particles in front of the catalyst layer
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0278—Feeding reactive fluids
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
    • B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
    • B01J8/0476—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds
    • B01J8/048—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more otherwise shaped beds the beds being superimposed one above the other
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • 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
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • 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
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00522—Controlling the temperature using inert heat absorbing solids outside the bed
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/30—Details relating to random packing elements
    • B01J2219/304—Composition or microstructure of the elements
    • B01J2219/30416—Ceramic

Abstract

In an oxidation process in a shell and tube reactor (10), an improvement is disposing a short bed of packing material (30) about the tube (50) inlets. The short bed operates to direct contaminants derived from heat exchange media away from the headspace (20) and thus prevents formation of combustible gas mixtures.

Description

Method for oxidation and reactor with improvement feed system
Technical field
The present invention relates to use the improvement of the method for shell-and-tube reactor.More specifically, the present invention relates to use the short bed of packing material that the pollutant guiding of for example seepage of heat exchange medium or derivatives thereof is left the head space (headspace) of tubular reactor and prevented to form combustible gas mixture.
Background technology
Tubular reactor is usually used in exothermic reaction, and for example propylene oxidation becomes the manufacturing of acrylic acid reaction and maleic anhydride.Usually, acrylic acid manufacturing is two sections gas catalysis oxidation reactions of propylene.This method has adopted to contain to be useful on and has become first section reactor of first section catalyst of third rare aldehyde to be applicable to the second section reactor that third rare formoxy-is changed into acrylic acid second section catalyst with being equipped with propylene oxidation.Usually, being used to make acrylic acid mixed feeding reactant (for example propylene, air and steam) estimates not and can light being lower than under about 450 ℃ temperature.However, if feed reactants contains a large amount of pollutants, also spontaneous combustion can take place under relatively low temperature.This burning can damage equipment, with the waste the mode consumption of raw material or make and should continuous reaction cycle be interrupted, or the like.
At United States Patent (USP) 5,719, proposed adjustment and focus in 318 and suppressed.In this manufacturing acrylic acid, use the particle of all size, the particle that preferably contains catalyst comes focus or the accumulation of heat in the inhibitory reaction pipe catalyst layer.
United States Patent (USP) 4,921,681 disclose a kind of by filling in the pipe in catalyst downstream that inert particle reduces ethylene oxide loss and near the method for the risk of the uncontrolled partial combustion ethylene oxide reactor outlet.
United States Patent (USP) 5,080,872 disclose the method that a kind of use contains the solids bed conditioned reaction device internal temperature in various temperature district (reactant fluid is mutually by these humidity provinces).
United States Patent (USP) 6,028,220 disclose the oxidation of propylene, reduce focus in the catalyst layer by changing catalyst activity during this period; And
United States Patent (USP) 6,563,000 has described and has a kind ofly made acrylic acid by the third rare aldehyde, and it comprises a plurality of reaction zones, and is wherein such as everyone knows, and each reaction zone contains a kind of activity catalyst different with adjacent area.
Disclose by particulate matter being circulated control method of temperature, referring to, for example, United States Patent (USP) 4,594,967, it discloses the reaction of using in the circulation particulate control fluidized-bed reactor, calcium sulfide can also be changed into calcium sulfate simultaneously.United States Patent (USP) 4,672,918 disclose and make the solid circulation of controlled temperature control fluidized-bed temperature.United States Patent (USP) 4,899,695 disclose and have a kind ofly controlled the heat transfer in the fluidized bed combustion reactor and the method for erosion by particle is added (some particles can recycle thus) in the fuel element with the combustion reaction agent or under the situation that has the combustion reaction agent.United States Patent (USP) 5,505,907 described a kind of by in air-flow, add the applying solid particle, with these particles circulations and separate, their recirculation is reused controlled the inlet air flow method of temperature then.U.S. Patent application 2002/0191732 discloses the suspended solid control temperature of using circulation; U.S. Patent application 2002/0048537 discloses a kind of olefin polymerization process, wherein makes the solid particle circulation by compressor.In addition, used Ceramic Balls to fill the intersegmental space of two reactor to play the effect of thermoreceptor.
Yet above-mentioned prior art all fails to solve the problem that reactor feed is polluted or mixed.
For example, United States Patent (USP) 4,029,636 have described pollutant removal, it discloses by making waste gas remove the described method of molybdenum trioxide of the reactor exhaust that the reactor that contains catalyst with base of molybdenum produces through the cooling solid bed that is arranged in the tubular reactor port of export, and wherein molybdenum trioxide is deposited on the cooling solid bed.United States Patent (USP) 5,413,699 disclose by making and have contained NO xGas through DeNO xCatalyst bed removes NO xAt last, United States Patent (USP) 5,538,544 disclose a kind of pressure swing adsorption system, by this system gas are added the container top of this pressure swing adsorption system and owing to by classification ball bed supporting system it are evenly distributed on adsorbent bed.
The method that above-mentioned control is polluted requires environment and/or the structure and the application of to a certain degree specialization, therefore, they can not be used to improve existing equipment simply to limit the pollution under the reactor break situation for example, in this case, heat-exchange fluid will seepage and is formed derivative and mix with reactor feed.
Summary of the invention
The present invention part is based on following discovery: near short of the packing material the reactor tube inlet of shell-and-tube reactor can limit decomposition gas (NO just x) from heat exchange medium, move to the reactor head space.Have been found that this is provided with the spontaneous combustion problem that is caused by the heat exchange medium seepage of almost having eliminated.Have been found that short bed is enough to improve contaminant problems, and do not need to use darker bed and relevant pressure drop and material consumption thereof.
Usually, the present invention relates to the high-temperature oxidation of improved gaseous reactant in containing the shell-and-tube reactor of a plurality of reactor tubes, wherein reactor tube is immersed in the heat exchange medium contained in the shell, and thus the inner space and the heat exchange medium of reactor tube is separated.Usually, near feed plenum with characteristic cross-sectional area (plenum) or the head space that inner inlet of reactor tube and reactor tube inlet is links to each other (the reactor tube inlet can not stop up usually), and the speed that enters the feed gas mixture of reactor tube inlet like this is the volumetric rate of the flow of feed gas mixture divided by near the characteristic cross-sectional area gained of the plemum the reactor tube inlet.This method also comprises feed gas mixture is added the reactor tube from plemum.Improvement of the present invention comprises makes the short bed next-door neighbour of packing material reactor tube inlet.This weak point bed can comprise that about 0.3 to about 0.75 voidage is to improve near the speed of the feed gas mixture of reactor tube inlet, during near the reactor break reactor tube inlet (its at heat exchange medium because corrosion between pipe and end plate, may take place during seepage), control of the pollution of the decomposition gas of heat exchange medium thus to feed plenum.Usually, lack a volume that occupies less than 20% of head space volume, and preferred less than about 10% of head space volume.
Preferably, packing material comprises that diameter is about 0.125 to about 4 inches spherical macroparticle.Most preferably diameter is less than about 2 inches ceramic macroparticle.Other packing material shape can be selected from the plate-like of ball sheet, disk shape, shaft-like and different shape.Especially preferably available from Norton (Akron, OH, DENSTONE  ball USA).Method and apparatus of the present invention can be used for making methacrylic acid, maleic anhydride, acrylic acid and contingent other parts oxidation in for example oxirane or vinyl acetate monomer manufacturing.
In another aspect of this invention, provide a kind of improvement to shell-and-tube reactor, this reactor contains the pipe in the heat exchange medium that is immersed in 200-400 ℃, and this improvement comprises the short bed of packing material that adds as described below near reactor tube.This weak point bed accessory has about 10 to about 25 inches degree of depth, and reactor tube has about 0.75 to about 2 inches diameter in preferred embodiment.Improved reactor is applicable to acrylic acid manufacturing as described below.
Control impurity, for example the oxidant of nitrogen oxide and so on just can control spontaneous combustion flammable and that do not expect.When feed gas mixture and pollutant had higher flammable mixture in conjunction with formation, enough flow velocitys can prevent temperature excursion.Therefore, this bed setting can prevent that pollutant from moving in the head space undesirably, and no matter whether this pollutant has improved combustibility.For example, pollutant can be a catalyst poison, thus, is prevalent in head space thereby this pollutant need be limited in the regional area of reactor and enters in all pipes.
According to as detailed below and according to claim, other features and advantages of the present invention are conspicuous.
Description of drawings
Fig. 1 is the schematic diagram of expression method and apparatus of the present invention.
The spontaneous combustion of the inlet air flow when Fig. 2 represents to have 0.2%NO.
Similar reference symbol is represented similar elements among each figure.
The specific embodiment
Usually, in exothermic reaction, use the steel tube shell type reactor that contains heat exchange medium to remove reaction heat.In the method for unusual high temperature, use salt to remove reaction heat as heat exchange medium.Be not entangled in theory, the applicant believes, the anion of the salt in the heat exchange medium can with the iron oxide reaction that forms on the reactor tube.As J.C.Casanova, " Thermal decomposition ofsodium nitrate; Part I-Thermogravimetric study, with data of the reaction ofnitric oxide with sodium oxide.Part II-Systematic analytical study of thereaction in the presence of iron oxide "; Bull.Soc.Chim; France (1959) pp.429-440 (it is incorporated herein by this reference fully) is described; anion; for example, nitrate anion and nitrite anions can decompose the generation nitrogen oxide when having iron oxide in the seepage zone.Nitrogen oxide especially can comprise nitric oxide (NO), nitrous oxide (N 2O) and nitrogen dioxide (NO 2).A small amount of nitrogen oxide that exists, for example 10 to 9000ppm, can play the effect of oxidant and reduce heat exchange medium the temperature that issuable feed gas mixture is caught fire when infiltrating head space.For example, the feed gas mixture of 7% propylene/60% air/30% steam is stable under about 450 ℃.Exist the nitrogen oxide of 5000ppm ignition temperature can be reduced to for example 300 ℃.The existence of the short bed of packing material of next-door neighbour's reactor tube inlet can prevent that pollutant from moving to head space, perhaps extinguish the spontaneous combustion when having nitrogen oxide, reduce flammable mixture in reactor the time of staying or pollutant is limited in the zone that seepage takes place, perhaps selectively change the Temperature Distribution of reactor.Regardless of theory, short bed has been found remarkably effective in improving the spontaneous combustion problem.
" macroparticle " used herein is volume for about at least 0.015 milliliter or bigger, is preferably greater than about 0.1 milliliter or bigger any solid three-dimensional object.Only for reference, 1/4 " the diameter spherolite has about 0.13 milliliter volume.
" voidage " used herein is the volume in the gap in material bed and the ratio of bed cumulative volume (material adds free space wherein).
With reference to accompanying drawing, Fig. 1 represents shell-and-tube reactor 10, and it comprises the short bed 30 of top 15, packing material, heat exchange shell 40 and a plurality of reactor tube 50 that is arranged in reactor that defines feed plenum or head space 20.Feed plenum comprises and is used for the distributor 60 that the reactant to feed gas mixture mixes.Feed plenum 20 links to each other with a plurality of reactor tubes 50 in the heat exchanger 40 by end plate 55.The size of feed plenum or head space 20 can be with the cross-section variation of the reactor tube in the reactor 10.For example, feed plenum can be about 5 to about 14 feet high, and the diameter of feed plenum is about 2 to about 20 feet.The a plurality of reactor tubes 50 that have reactor tube inlet 70 are surrounded by heat exchange medium 80.For example, heat exchange medium 80 can be a salt.Usually, coolant salt can comprise molten salt bath.Suitable salt comprises potassium nitrate, potassium nitrite, natrium nitrosum and/or sodium nitrate or low-melting-point metal, for example the alloy of sodium, mercury or various metals.The temperature of heat exchange medium can be lower than 450 ℃, more preferably about 420 ℃.Particularly, can use the HITEC salt of Dupont, it comprises about 53% potassium nitrate, about 40% sodium nitrate and about 7% sodium nitrate.Under the situation of reactor break,, enter feed plenum 20 because the pollutant that is decomposed to form of anion in the coolant salt can infiltrate end plate area 65.Salt is considered at first seepage, decomposes under the situation that has rust and oxidation catalyst then.
Packing material 30 short bed next-door neighbour reactor tube inlets 70 horizontal-extending in plemum.Short bed 30 comprises for example discrete inert macroparticles of ceramic material.The short bed of packing material 30 size variables.The suitable depth H of short bed can be lower than about 24 inches, but is at least 5 inches; Usually about 1 foot.The shape of these inert macroparticles is not crucial.For example, macroparticle can be granular, and for example spheroid, ball sheet, disk, hollow tube, spherical, cylindric, ring-type maybe can be shaft-like, plate-like and mesh-like, or the aggregation of above-mentioned shape.Suitable macroparticle can be a spheroid.When using granular or other inert substance, their size needn't be consistent.Yet when using sphere inert substance, sphere diameter can be about 1/16 inch to about 2 inches, preferably approximately 0.25 inch diameter preferably.It should be noted that the size of macroparticle is most preferably not exceeding the diameter of reactor tube in the reactor, and (about 1 ") can not stopped up reactor tube like this.
Short bed 30 has sufficient voidage, thereby can not cause too big pressure drop differential pressure during by reactor tube in feed gas mixture.The voidage of macroparticle is about 0.25 to about 0.75 in the short bed 30, preferably approximately 0.3 to 0.5, most preferably 0.4.The packed density of macroparticle is about 70 pounds/inch 3To about 110 pounds/inch 3, usually about 80-90 pound/inch 3Particularly, spheroid can be, for example, and Norton Chemicals (Akron, OH, USA) the DENSTONE  spheroid of Chu Shouing.In the various specific embodiment, DENSTONE  spheroid can be, for example, and DENSTONE  57, DENSTONE  2000 or DENSTONE  99.Macroparticle can be pottery, aluminium oxide, silica or clay on forming.
The short bed 30 of packing material has improved the speed of the feed gas mixture that enters the reactor tube inlet, because the cross section that provides for fluid has been provided the area that macroparticle occupies.The speed of this feed gas mixture improves to make owing to the break pollutant (for example nitrogen oxide) of oxidant of entering reactor tube 50 and so on of end plate just was eliminated before moving to plemum.Flow velocity and streamlined flow path can reduce the combustibility in the feed plenum 20 fully, may mix the spontaneous combustion that causes feed gas mixture in this feed gas mixture and pollutant.Can under the time that is less than the spontaneous combustion required time, control spontaneous combustion by making feed gas mixture by reactor tube.
Generally speaking, described use shell-and-tube heat exchange type reactor and in the two-stage catalytic oxidizing process, made acrylic acid by propylene.Referring to, for example, United States Patent (USP) 6,545,178,6,482,981 and 6,069,271, they are incorporated herein by this reference fully.
Refer again to Fig. 1, in the method for making these products, distributor 60 is transported to the feed gas mixture of reactant in feed plenum or the head space 20.Feed gas mixture expands and enters feed plenum 20 and enter the short bed 30 of packing material by it.The superficial linear velocity in a column that enters the feed gas mixture of feed plenum can be 3 to 10 feet per seconds.For example, feed gas mixture can comprise 7% propylene/60% air/30% steam.Feed gas mixture enters the short bed 30 of packing materials with the reactor tube of reactor inlet 70 next-door neighbours.The VELOCITY DISTRIBUTION of size that can be by tubular reactor, the air-flow mixture of the inlet plemum of flowing through, required pressure drop and short bed is determined the packing material of the best.
In another embodiment of the present invention, with reference to Fig. 1, the feed gas mixture that comprises normal butane and air enters feed plenum 20 by distributor 60.Feed gas mixture evenly distributes on the short bed 30 of packing material and feeds reactor tube 50.By reactor 10 time, normal butane and the reaction of airborne oxygen produce maleic anhydride.
In the another specific embodiment of the present invention, referring to Fig. 1, the feed gas mixture that comprises isobutene and air enters feed plenum 20 by distributor 60.Feed gas mixture evenly distributes on the short bed 30 of packing material and feeds reactor tube 50.By reactor tube the time, isobutene and the reaction of airborne oxygen produce methacrylic acid.
Can make other products according to the present invention, for example vinyl acetate or oxirane.
Further set forth feature of the present invention by the following example, they only are used to illustrate the present invention and unrestricted the present invention.
Comparative Examples
Propylene oxidation is being become in the acrylic acid, at 620 °F; 326 ℃ temperature and about 16psig; 1.1 the pressure of crust specification contains the tubular reactor of a plurality of reactor tubes down with the feed gas mixture operation that consists of about 7% propylene, about 60% air and about 30% steam, wherein the cross-sectional area of reactor tube is (about 60 square feet of open tube areas; About 200 square feet of topside areas), length is 20 feet (comprising cooled region).Make this System Operation, to obtain the air-flow of about 1200MSCFH.Reactor shows leakage problems, and wherein the pollutant that enters the reactor head space from heat exchange medium has changed the combustibility of charging.Because spontaneous combustion has taken place the gas feed mixture in the head space, reactor shuts down.Reactor tube is cooled off in salt cooling bath with Dupont HITEC salt, and this salt is considered to a kind of pollution sources.
Embodiment 1
Adding DENSTONE  1/4 " the short bed of the packing material of spheroid in the reactor of above-mentioned Comparative Examples.The degree of depth of the short bed of packing material is 1 foot.It mainly is about 620 °F that the selecting reactor condition makes in the reactor; 326 ℃ temperature and about 16psig; 1.1 the pressure of crust specification, feed gas mixture consist of about 7% propylene, about 60% air and about 30% steam.Make this System Operation, to obtain the air-flow circulation volume of about 1200MSCFH.Placed near the reactor tube inlet by lacking bed, the charging spontaneous combustion is eliminated substantially, and yield and conversion ratio are constant.
Embodiment 2
Use improved ASTM G72-82 (in 1996 again by) evaluation and test to have the spontaneous combustion of the feed gas mixture of the propylene/air/water under the nitrogen oxide situation.The sample of feed gas mixture that in having one liter of rustless steel container of hoop heater, adds 6.7 propylene, 61.3% air, 31.8 steam and 0.2%NO.As shown in Figure 2, monitor temperature (℃) with the time (minute) and the functional relation of pressure (crust).With reference to Fig. 2, the result shows at about 280 ℃ spontaneous combustions takes place, and it is still not flammable at 450 ℃ not contain the feed gas mixture of NO.
Other specific embodiment within the scope of the appended claims.

Claims (22)

1. the high-temperature oxidation of the gaseous reactant in containing the shell-and-tube reactor of a plurality of reactor tubes, wherein reactor tube is immersed in the heat exchange medium contained in the shell, and thus the inner space and the heat exchange medium of reactor tube are separated, and wherein the inner inlet of reactor tube links to each other with near the reactor tube inlet the feed plenum with characteristic cross-sectional area, and the reactor tube inlet can not stop up usually, the speed that enters the feed gas mixture of reactor tube inlet like this is the volumetric rate of the flow of feed gas mixture divided by near the characteristic cross-sectional area gained of the plemum the reactor tube, this method generally includes feed gas mixture is added the reactor tube from plemum, and improvement comprises:
Make the short bed next-door neighbour of packing material reactor tube inlet, the volume that its short-and-medium bed occupies is less than about 20% of feed plenum volume; And
Its short-and-medium bed accessory has about 0.3 to about 0.75 voidage, and can effectively improve near the speed of the feed gas mixture the reactor tube inlet thus, thereby under the situation that near the device that reacts the reactor tube inlet breaks, can control the pollution of heat exchange medium to feed plenum.
2. the method for claim 1, wherein packing material comprises macroparticle.
3. the method for claim 1, wherein the diameter of each macroparticle is about 0.125 to about 4 inches.
4. method as claimed in claim 3, wherein the diameter of each macroparticle is less than about 2 inches.
5. the method for claim 1, wherein macroparticle comprises ceramic macroparticle.
6. method as claimed in claim 2, wherein macroparticle is spherical substantially and has about 0.125 to about 4 inches diameter.
7. method as claimed in claim 2, wherein macroparticle is selected from spheroid, ball sheet, hollow tube, rhabodoid and discoid body.
8. method as claimed in claim 7, wherein macroparticle is a spheroid.
9. method as claimed in claim 8, wherein spheroid is the DENSTONE ball.
10. method as claimed in claim 9, wherein the DENSTONE ball is selected from DENSTONE 57, DENSTONE 2000 or DENSTONE 99.
11. the method for claim 1, wherein oxidation reaction comprises isobutylene oxidation is become methacrylic acid.
12. the method for claim 1, wherein oxidation reaction comprises butane oxidation is become maleic anhydride.
13. the method for claim 1, wherein oxidation reaction comprises the oxidation of propylene.
14. the method for claim 1, wherein heat exchange medium is the fuse salt cooling agent.
15. method as claimed in claim 14, wherein salt is HITEC salt.
16. method as claimed in claim 15, wherein salt is about 53% potassium nitrate, about 40% sodium nitrate and about 7% sodium nitrate.
17. the method for claim 1, the volume that its short-and-medium bed occupies is less than about 10% of feed plenum volume.
18. in shell-and-tube reactor, carry out the device of the high-temperature oxydation of gaseous reactant, it is configured to make feed gas mixture to flow in the tubular reactor through distributor, and feed gas mixture is directed to a plurality of reactor tubes from the reactor tube inlet of feed plenum by linking to each other with feed plenum, reactor tube be immersed in about 200 ℃ to about 400 ℃ heat exchange medium, improvement comprises:
The short bed of packing material of next-door neighbour's reactor tube inlet, wherein this weak point bed accessory has about 0.3 to about 0.75 voidage, under the situation that near the device that reacts the reactor tube inlet breaks, can control of the pollution of any decomposition gas of heat exchange medium thus, and the volume that its short-and-medium bed occupies is less than about 20% of feed plenum volume to feed plenum.
19. as the device of claim 18, wherein the diameter of each reaction tube is about 0.75 inch to about 2 inches.
20. as the device of claim 18, wherein the degree of depth of the short bed of packing material is about 10 inches to about 25 inches.
21. as the device of claim 20, the degree of depth of its short-and-medium bed is at least 10 inches.
22. make acrylic acid at the shell-and-tube reactor that is used for propylene oxidation, comprise and make feed gas mixture enter feed plenum by distributor, and with feed gas mixture from feed plenum is directed to a plurality of reactor tubes the shell-and-tube reactor, reactor tube be immersed in about 200 ℃ to about 400 ℃ fuse salt cooling agent, improvement comprises:
The reactor tube inlet of next-door neighbour's reactor tube provides packing material short bed, and wherein this weak point volume that occupies is less than about 20% of feed plenum volume; And
Feed gas mixture and short bench grafting are touched.
CN03826973.2A 2003-07-31 2003-07-31 Oxidation process and reactor with modified feed system Pending CN1819869A (en)

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