CN100439313C - Multistage fluidized bed reactor for preparing propenoic acid from propene oxidation and preparing method - Google Patents
Multistage fluidized bed reactor for preparing propenoic acid from propene oxidation and preparing method Download PDFInfo
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- CN100439313C CN100439313C CNB2006101140921A CN200610114092A CN100439313C CN 100439313 C CN100439313 C CN 100439313C CN B2006101140921 A CNB2006101140921 A CN B2006101140921A CN 200610114092 A CN200610114092 A CN 200610114092A CN 100439313 C CN100439313 C CN 100439313C
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Abstract
The present invention belongs to the field of chemical technology, and is multistage fluidized bed reactor for oxidizing propylene into propenoic acid and the preparation process therein. The reactor includes several fluidized bed reaction stages, material gas inlet, gas distributor, expansion section, the second step reaction device, etc. Into each of the fluidized bed reaction stages, catalyst is added, and air, nitrogen, propylene and water steam are introduced, so as to react under controlled temperature. The gaseous product propenoic acid is obtained through separating the product of the expansion section of the second step reaction device. The reactor of the present invention has gas distributor with excellent gas distributing effect, metal oxide catalyst with high activity and plug flow like characteristic, so that it possesses greatly raised gas-solid contact effect, high propylene converting rate and other advantages.
Description
Technical field
The present invention relates to a kind ofly prepare acrylic acid equipment and processing method, belong to chemical engineering process and equipment technical field by propylene and air reaction.
Background technology
Contain unsaturated double-bond and polar molecular structure in the molecule of vinylformic acid and ester thereof, can be built into thousands of polymkeric substance, thereby be widely used in fields such as coating, chemical fibre, weaving, tackiness agent, papermaking, leather, modifying plastics, sanitary material, agriculture water conservation with various performances.Along with the demand growth of High hydrophilous resin and coating, the demand of vinylformic acid and ester thereof sharply increases.
The suitability for industrialized production acrylic acid has 5 kinds, i.e. oxidation of propylene, improvement Reppe method, acrylonitrile hydrolysis method, cyanoethanol method and ketenes method.All once as the main method of producing vinylformic acid and ester thereof, back two kinds of methods are eliminated because efficient is low, energy consumption is big these methods.The acrylonitrile hydrolysis method is only limited to produces MA, EA.When producing senior ester, also need further to adopt ester-interchange method.Improvement Reppe method once once dominated in Coal Chemical Industry developing period.So far still have some enterprises to adopt acrylonitrile hydrolysis methods and improvement Reppe method, but in recent years in the world new device all trend towards adopting oxidation of propylene.
The oxidation of propylene of industrial present employing all is that the propylene two-step oxidation style prepares vinylformic acid, and the principle of reaction is that the first step propylene initial oxidation is a propenal, and the second step propenal further is oxidized to vinylformic acid, and the reactor that is adopted is fixed-bed reactor.The propylene two-step oxidation style prepares acrylic acid technology and mainly contains Japanese catalyst technology, BASF technology and Mitsubishi oiling technology.And in China, what the acrylic acid process of suitability for industrialized production adopted all is external technology basically, so the described reactor of this patent and technology all have very big development space in the China and even the world.
Prepare acrylic acid principle according to the propylene partial oxidation, this reaction belongs to strong exothermal reaction, industrial common employing calandria type fixed bed reactor, high density of propylene, operating restraint are within the limits of explosion scope of propylene, simultaneously, because the limitation of fixed bed itself, as: bad, the required heat interchanging area of thermal conduction is big etc., makes the calandria type fixed bed reactor temperature runaway easily, not only causes the reactor temperature skewness, catalyst deactivation, the safety coefficient of more feasible operation is low.For the safety coefficient that does not allow catalyst deactivation and improve operation, industrial when loading catalyst, the layering catalyzer of packing in each section reactor, and at topmost filling inertia bead, the purpose of doing like this is exactly in order to make propylene and air admission reactor can produce Gradient distribution from top to bottom afterwards, avoid moving on the hot(test)-spot temperature, produce temperature runaway and the danger that causes because too fierce in reactor top reaction.
For fear of above-mentioned shortcoming, propylene oxidation prepares the improvement of acrylic acid technology by fixed bed device and for example is disclosed in EP0911313A1, WO2005/011858A1, and WO2004/085363A1 is among the WO2005/115617A1.Yet known method is not still broken away from and is conducted heat badly in the technology of fixed bed, causes the danger of temperature runaway easily.
On the other hand, uniformity of temperature profile in the good heat-transfer of fluidized-bed, beds, using fluidized-bed also is known as the reactor of strong exothermal reaction.Therefore, a kind of technology of using fluidized-bed reactor to produce vinylformic acid and methacrylic acid has been described among the US2004/0092768A1, but it focuses on the improvement and the preparation of catalyzer, and purpose is in order to keep the high yield of vinylformic acid and methacrylic acid for a long time.WO2006/072682A1 has described and has a kind ofly produced acrylic acid by propane in fluidized-bed reactor, but the transformation efficiency of propane low (＜30%).Sohio, BP821,999 proposed the employing single-stage fluidized bed in 1958 carries out the reaction of this alkene part catalyzed oxidation, but the catalyst technology, fluidized bed gas sparger technology and the fluidized-bed that are limited at that time amplify problems such as imperfection, make propylene conversion very low (＜60%), liquid yield yet not high (＜70%) does not have very high industrial application value.Therefore, if a kind of good heat-transfer of device can be arranged, the reaction liberated heat in time can be removed, make that reactor temperature is evenly distributed in reaction process, simultaneously, react for this, the transformation efficiency of raw material propylene is very high, liquid propylene aldehyde and acrylic acid selectivity are fine again, then should be able to have good commercial application value.
Summary of the invention
The objective of the invention is to prepare in acrylic acid process at existing propylene two-step oxidation, the easy temperature runaway of the fixed-bed reactor that adopted, shortcomings such as the safety coefficient of the bad control of temperature, operation is low provide a kind of multistage fluidized bed that adopts new and effective gas distributor to carry out propylene and air reaction is produced acrylic acid device and processing method.In multistage fluidized bed, react, not only can make propylene conversion higher, and the throughput height of reactor, turndown ratio are big, the selectivity height of liquid phase, simultaneously, have also that catalyst consumption is few, a less investment, low power consumption and other advantages.
Technical scheme of the present invention is as follows:
1, a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation comprises that the device and the second step acrolein oxidation that the first step propylene oxidation prepares acrolein reaction prepare the device of vinylformic acid reaction, is characterized in that this reactor comprises:
(a) multistage fluidized bed main equipment, the series connection between the fluidized-bed main equipment constitute the first step reaction unit and the second step reaction unit respectively, connect with flange between every grade of main equipment;
(b) four reactor feed gas inlets that link to each other with first step fluidized-bed main equipment barrel in the first step reaction unit are respectively a propylene inlet, a gas inlet, and a nitrogen inlet and a steam entry:
(c) preheating section in the reactor feed gas ingress;
(d) gas distributor that is arranged on the gas distributor on preheating section top and is arranged on respective fluidized beds main equipment bottom, gas distributor links to each other with the barrel of fluidized-bed main equipment;
(e) expanding reach that is arranged on behind the first step reaction unit, the inlet of this expanding reach links to each other with the fluidized-bed main equipment of the first step reaction unit, and one be arranged on second expanding reach of step behind the reaction unit, the fluidized-bed main equipment of this expanding reach and the second step reaction links to each other, and is connected with flange between expanding reach and the main equipment;
(f) gas inlet, the first step reaction back that is arranged on first fluidized-bed main equipment bottom of the second step reaction unit, this inlet links to each other with the outlet of the expanding reach of the first step reaction, and first fluidized-bed main equipment bottom of the second step reaction unit also has an air unstripped gas inlet;
(g) pneumatic outlet that is arranged on the expanding reach top of the second step reaction unit.
Described multistage fluidized bed is to be combined in series by a plurality of fluidized-bed main equipments.
Described gas distributor is any in variable mass drift tube type sparger, multiaperture-type sparger, the float-valve type sparger.
The pressure drop of described gas distributor is 20%～35% of a beds total pressure drop, and the ratio that is not more than the bubble of 4mm by diameter in the incipient bubble of its generation is 75%～90%.
Described expanding reach separation efficiency can reach more than 98.0% by the design of its diameter, the minimum catalyst particle size that reclaims is 4 μ m, the fluidized-bed main equipment upper extension section of the first step reaction can be avoided the catalyst mix of one, two two-step reactions, and the fluidized-bed main equipment upper extension section of second step reaction can be avoided the liquid-phase product of thin catalyst contamination subsequent recovery.
In order to suppress the coalescence trend of bubble in uphill process, increase the gas-solid contact efficiency, improve propylene conversion, two-step reaction of the present invention all uses multistage fluidized bed, make and carry out under the operational condition of plug flow approaching, not only can improve propylene conversion, and make relative with acrylic acid selectivity higher propenal.
In order to guarantee the high conversion of propylene, avoid the cold conditions charging, the present invention uses and in the unstripped gas ingress preheating section is set, and makes the raw material feeding temperature at 200～250 ℃.
In order to guarantee the high conversion of propylene, the present invention uses the gas distributor of high pressure drop to carry out the gas initial distribution, controls its fluidized state.The pressure drop of gas distributor is 20%～35% of a bed total pressure drop, and the ratio that is not more than the bubble of 4mm by diameter in the incipient bubble of its generation is 75%～90%.The form of gas distributor comprises variable mass drift tube type sparger, multiaperture-type sparger, float-valve type sparger.
In order to guarantee that the second step acrolein oxidation prepares acrylic acid reacting completely, in the first step fluidized-bed main equipment of second step reaction, continue bubbling air, make that residual oxygen is not less than 3% in the tail gas after the two-step reaction.
Gone out by gas-entrained for fear of the first step catalyst for reaction, pollution second step reaction and the second step catalyst for reaction are gone out by gas-entrained, the gas absorbing device of contaminate subsequent and the loss of catalyzer, the present invention uses expanding reach to carry out catalyst recovery, its efficient is greater than 98.0%, and the catalyst particle size of recyclable minimum is 4 μ m.
Simultaneously, in order to guarantee good fluidized state, propylene conversion and propenal and acrylic acid selectivity and the wearing and tearing that reduce catalyzer, the first step catalysts that uses among the present invention is Mo-Bi/SiO
2O composite metallic oxide catalyst, particle diameter is 0.08～0.12mm, specific surface area is 8～13m
2/ g; The second step catalysts is Mo-V/SiO
2O composite metallic oxide catalyst, particle diameter is 0.08～0.12mm, specific surface area is 4～8m
2/ g.
Simultaneously, provide a kind of and utilized above-mentioned multistage fluidized bed reactor propylene oxidation to prepare method for producing acrylic acid, this preparation method comprises the steps:
(1): the fluidized-bed main equipment is linked to each other, and gas inlet, gas distributor, expanding reach link to each other with the fluidized-bed main equipment successively, and pneumatic outlet links to each other with expanding reach, constitutes complete multistage fluidized bed reactor;
(2): the catalyzer of above-mentioned two-step reaction is respectively charged in the fluidized-bed main equipments at different levels of the first step reaction and the reaction of second step, is deposited in the zone of gas distributor top in the fluidized-bed main equipments at different levels, form the emulsion zone of catalyzer; The static loading height of catalyzer is 1～2 times of fluidized-bed main equipment diameter;
(3): bubbling air and nitrogen, make the catalyzer in the fluidized-bed main equipment be in fluidized state, and heat main equipment with tile, make the first step catalyst for reaction emulsion zone temperature reach 300～320 ℃; The second step catalyst for reaction emulsion zone temperature reaches 200～220 ℃;
(4): by propylene with steam entry feeds propylene respectively and water vapour reacts;
(4.1): with the temperature of catalyzer emulsion zone in every grade of fluidized-bed main equipment of temperature control control the first step reaction at 330～375 ℃; The mol ratio of oxygen and propylene is 1.3～2.0 in the air; The mol ratio of water vapour and propylene is 0～3.5; Reactor feed gas cumulative volume air speed is 400～600Lh
-1Kg
-1, propylene cumulative volume air speed is 15～60Lh
-1Kg
-1With nitrogen adjustments of gas flow, make operating gas velocity actual in the fluidized-bed main equipments at different levels reach 0.03～0.05m/s;
(4.2): simultaneously, go on foot the temperature of catalyzer emulsion zone in the every grade of fluidized-bed main equipment that reacts at 270～320 ℃ with temperature control control second; Gas inlet from the fluidized-bed main equipment of second step reaction continues bubbling air, will increase air flow quantity in the reaction of two steps when the gas outlet oxygen content that detects the reaction of second step is lower than 3%;
(5): the part catalyzer in the last step fluidized-bed main equipment of the first step reaction unit in the catalyzer emulsion zone is carried into fluidized-bed main equipment top by air-flow, gaseous product (comprising principal product propenal, by product formaldehyde, acetate etc. and unreacted unstripped gas) and catalyzer process expanding reach after separating, gaseous product goes out fluidized-bed main equipment to the second step reaction fluidized-bed main equipment, and catalyzer returns the emulsion zone of catalyzer in the last step fluidized-bed main equipment; Part catalyzer in the last step fluidized-bed main equipment of the second step reaction unit in the catalyzer emulsion zone is carried into fluidized-bed main equipment top by air-flow, gaseous product and catalyzer are through the expanding reach after separating, gaseous product goes out the fluidized-bed main equipment, catalyzer returns the emulsion zone of catalyzer in the last step fluidized-bed main equipment, and wherein gaseous product obtains purpose product vinylformic acid after passing through follow-up absorption and rectifying program.
Propylene provided by the invention and air reaction prepare acrylic acid multistage fluidized bed, adopted the better gas distributor of gas distribution effect, and active preferred metal oxide catalyst, simultaneously, multistage fluidized bed has the feature that is similar to plug flow, make that the effect of gas-solid contact strengthens greatly in multistage fluidized bed, promoted the conversion of propylene.Simultaneously, in the temperature control process of reactor, slowly feed the amount of raw material propylene, the good heat transfer performance makes reaction heat in time to remove in fluidized-bed, the uniformity of temperature profile in the reactor, and it is higher to generate liquid phase propenal and acrylic acid selectivity.In the outlet of reactor, adopted high efficiency expanding reach to suppress catalyzer and carried away by air-flow, make that the acrylic acid purity of generation is higher.
And the present invention is compared with prior art, has the following advantages and beneficial effect:
(1) with present fixed bed in widely used large granular catalyst (diameter 5～8mm, high 5～8mm) compare, the median size of granules of catalyst is 0.08～0.12mm among the present invention, there is not the granule interior overheating problem, can suppress the loss of the activity component metal Mo in the catalyzer, improve life of catalyst, simultaneously because there is not the hole inside diffusional resistance basically in short grained catalyzer, the activity of such catalysts height, catalyzer is effective with contacting of reactor feed gas.
(2) compare with traditional fixed-bed reactor, when reaching changing effect identical with fixed bed and throughput, use reactor of the present invention and technology significantly to reduce catalyst consumption, investment cost is few.
(3) multistage fluidized bed reactor among the present invention is than the heat-transfer capability height of traditional fixed-bed reactor, the uniformity of temperature profile in reaction process, and the safety coefficient of operation increases, and has reduced operation instrument and regulate expenditure.
(4) multistage fluidized bed reactor among the present invention is compared with single fluidized bed reactor, and the unstripped gas propylene conversion increases, and has reduced follow-up gas separation unit, and the facility investment expense reduces.
(5) compare with traditional fixed-bed process, the fine particle of fluidized-bed reactor inactivation is easier to exchange, can be delivered to regenerating unit at short notice, saves manually, is beneficial to environmental protection.
Description of drawings
Fig. 1 is a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation structural representation of the present invention;
Among the figure: 1. catalyzer emulsion zone; 2. gas distributor; 3. reactor feed gas preheating section; 4. reactor feed gas enters the mouth; 5. the expanding reach of the first step reaction; 6. the first step is reacted the gas inlet, back; 7. second go on foot the gas inlet that reacts; 8. second go on foot the expanding reach that reacts; 9. second go on foot reaction gas outlet.
Embodiment
Specify the present invention below in conjunction with accompanying drawing.
Fig. 1 is a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation structural representation of the present invention; Among the figure: 1. catalyzer emulsion zone; 2. gas distributor; 3. reactor feed gas preheating section; 4. reactor feed gas enters the mouth; 5. the expanding reach of the first step reaction; 6. the first step is reacted the gas inlet, back; 7. second go on foot the gas inlet that reacts; 8. second go on foot the expanding reach that reacts; 9. second go on foot reaction gas outlet.It comprises: multistage fluidized bed main equipment, the series connection between the fluidized-bed main equipment constitute the first step reaction unit and the second step reaction unit respectively, connect with flange between every grade of main equipment; Four reactor feed gas inlets that link to each other with first step fluidized-bed main equipment barrel in the first step reaction unit are respectively a propylene inlet, a gas inlet, a nitrogen inlet and a steam entry; Preheating section in the reactor feed gas ingress; A gas distributor that is arranged on the gas distributor on preheating section top and is arranged on respective fluidized beds main equipment bottom, gas distributor links to each other with the barrel of fluidized-bed main equipment; An expanding reach that is arranged on behind the first step reaction unit, the inlet of this expanding reach links to each other with the fluidized-bed main equipment of the first step reaction unit, and one be arranged on second expanding reach of step behind the reaction unit, the fluidized-bed main equipment of this expanding reach and the second step reaction links to each other, and is connected with flange between expanding reach and the main equipment; A gas inlet, the first step reaction back that is arranged on first fluidized-bed main equipment bottom of the second step reaction unit, this inlet links to each other with the outlet of the expanding reach of the first step reaction, and first fluidized-bed main equipment bottom of the second step reaction unit also has an air unstripped gas inlet; A pneumatic outlet that is arranged on the expanding reach top of the second step reaction unit.
In fluidized-bed main equipments at different levels, be respectively charged into corresponding catalyzer, the static loading height of catalyzer is about 1～2 times of main equipment diameter, after catalyzer has all loaded, 4 difference bubbling air and the nitrogen from the gas inlet, air and nitrogen are through entering in the first step fluidized-bed main equipment of the first step reaction after preheating section 3 and the gas distributor 2, simultaneously, under catalyzer is in fluidized state, heat the main equipment of each step reaction with tile, the temperature that makes catalyzer emulsion zone in the fluidized-bed main equipments at different levels of the first step reaction is at 300～320 ℃, the temperature of catalyzer emulsion zone is at 200～220 ℃ in the fluidized-bed main equipments at different levels of second step reaction, after reaching, temperature feeds another kind of reaction raw materials propylene gradually and bubbling air in the first step fluidized-bed main equipment of second step reaction, and the adjusting temperature control, the temperature that makes catalyzer emulsion zone in the fluidized-bed main equipments at different levels of the first step reaction is at 330～375 ℃; The mol ratio of oxygen and propylene is 1.3～2.0 in the reaction of the control the first step, and the mol ratio of water vapour and propylene is 0～3.5, and the unstripped gas cumulative volume air speed of the first step reaction is 400～600Lh
-1Kg
-1, propylene cumulative volume air speed is 15～60Lh
-1Kg
-1, simultaneously, control second temperature that goes on foot catalyzer emulsion zone in the fluidized-bed main equipments at different levels that react at 270～320 ℃ with temperature control, to guarantee in the reaction process that operating gas velocity is at 0.03～0.05m/s in the fluidized-bed main equipments at different levels.
Basically can transform fully after the emulsion zone 1 of unstripped gas propylene through catalyzer, gas after the first step reaction is through the first step fluidized-bed main equipment inlet 6 of expanding reach 5 to the second step reaction of the first step reaction, gas after the reaction of second step is through 8 to second step of expanding reach reaction gas outlet 9, then through obtaining purpose product vinylformic acid behind follow-up absorption and the rectifier unit.
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 1.5 and 1 times of device diameters; The mol ratio of oxygen and propylene is 1.3 in the control air, anhydrous steam; Propylene cumulative volume air speed is 20Lh
-1Kg
-1, total gas volume air speed is 470Lh
-1Kg
-1Operating gas velocity during reaction is 0.03m/s; First step main equipment inner catalyst emulsion zone temperature is 330 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 340 ℃, and propylene conversion is 89.33%, and the liquid phase selectivity is 81.53%.
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 1.5 and 1 times of device diameters; The mol ratio of oxygen and propylene is 1.3 in the control air, anhydrous steam; Propylene cumulative volume air speed is 20Lh
-1Kg
-1, total gas volume air speed is 470Lh
-1Kg
-1Operating gas velocity during reaction is 0.04m/s; First step main equipment inner catalyst emulsion zone temperature is 370 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 360 ℃, and propylene conversion is 87.76%, and the liquid phase selectivity is 83.74%.
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 2 and 1 times of device diameters; The mol ratio of oxygen and propylene is 1.8 in the control air, anhydrous steam; Propylene cumulative volume air speed is 20Lh
-1Kg
-1, total gas volume air speed is 470Lh
-1Kg
-1Operating gas velocity during reaction is 0.04m/s; First step main equipment inner catalyst emulsion zone temperature is 365 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 350 ℃, and propylene conversion is 90.92%, and the liquid phase selectivity is 81.87%.
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 1.5 and 1 times of device diameters; The mol ratio of oxygen and propylene is 1.8 in the control air, and the mol ratio of water vapour and propylene is 1.7; Propylene cumulative volume air speed is 60Lh
-1Kg
-1, total gas volume air speed is 600Lh
-1Kg
-1Operating gas velocity during reaction is 0.05m/s; First step main equipment inner catalyst emulsion zone temperature is 375 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 365 ℃, and propylene conversion is 89.67%, and the liquid phase selectivity is 67.24%.
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 1.5 and 1 times of device diameters; The mol ratio of oxygen and propylene is 1.8 in the control air, and the mol ratio of water vapour and propylene is 2.3; Propylene cumulative volume air speed is 40Lh
-1Kg
-1, total gas volume air speed is 470Lh
-1Kg
-1Operating gas velocity during reaction is 0.04m/s; First step main equipment inner catalyst emulsion zone temperature is 375 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 350 ℃, and propylene conversion is 93.61%, and the liquid phase selectivity is 71.35%.
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 2 and 1 times of device diameters; The mol ratio of oxygen and propylene is 1.5 in the control air, and the mol ratio of water vapour and propylene is 3.5; Propylene cumulative volume air speed is 20Lh
-1Kg
-1, total gas volume air speed is 470Lh
-1Kg
-1Operating gas velocity during reaction is 0.04m/s; First step main equipment inner catalyst emulsion zone temperature is 375 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 370 ℃, and propylene conversion is 78.97%, and the liquid phase selectivity is 83.43%.
Embodiment 7
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 1.5 and 1 times of device diameters; The mol ratio of oxygen and propylene is 2.0 in the control air, anhydrous steam; Propylene cumulative volume air speed is 20Lh
-1Kg
-1, total gas volume air speed is 500Lh
-1Kg
-1Operating gas velocity during reaction is 0.04m/s; First step main equipment inner catalyst emulsion zone temperature is 365 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 345 ℃, and propylene conversion is 91.33%, and the liquid phase selectivity is 70.98%.
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); Adopt separation efficiency greater than 98.0% expanding reach; The use granularity is 0.08～0.12mm, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; The first step, second stage main equipment inner catalyst loading height are respectively 2 and 1 times of device diameters; The mol ratio of oxygen and propylene is 1.6 in the control air, anhydrous steam; Propylene cumulative volume air speed is 15Lh
-1Kg
-1, total gas volume air speed is 400Lh
-1Kg
-1Operating gas velocity during reaction is 0.04m/s; First step main equipment inner catalyst emulsion zone temperature is 365 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 350 ℃, and propylene conversion is 89.78%, and the liquid phase selectivity is 79.09%.
Embodiment 9
In multistage fluidized bed reactor as shown in Figure 1, in preceding two-step fluidized bed main equipment, carry out the first step reaction (being followed successively by the first step, second stage fluidized-bed main equipment from bottom to up); The first step fluidized-bed main equipment that reacts from pneumatic outlet to the second step behind the expanding reach that the reacted gas of the first step passes through with second stage fluidized-bed main equipment links to each other; It is 0.08～0.12mm that granularity is used in the first step reaction, and specific surface area is 12m
2The O composite metallic oxide catalyst of/g; It is 0.08～0.12mm that granularity is used in the reaction of second step, and specific surface area is 7m
2The O composite metallic oxide catalyst of/g; The first step, the second stage main equipment inner catalyst loading height of the first step reaction is respectively 1.5 and 1 times of device diameters; The main equipment inner catalyst loading height of second step reaction is 1 times of device diameters; The mol ratio of oxygen and propylene is 1.8 in the control air, anhydrous steam; Propylene cumulative volume air speed is 20Lh in the first step reaction
-1Kg
-1, total gas volume air speed is 475Lh
-1Kg
-1Operating gas velocity during reaction is 0.04m/s; The first step main equipment inner catalyst emulsion zone temperature of the first step reaction is 365 ℃, and second stage main equipment inner catalyst emulsion zone temperature is 360 ℃, and the main equipment inner catalyst emulsion zone temperature of second step reaction is 290 ℃; Through behind the two-step reaction, propylene conversion is 88.70%, and the liquid phase selectivity is 78.1%.
Claims (7)
1, a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation comprises that the device and the second step acrolein oxidation that the first step propylene oxidation prepares acrolein reaction prepare the device of vinylformic acid reaction, is characterized in that this reactor comprises:
(a) multistage fluidized bed main equipment, the series connection between the fluidized-bed main equipment constitute the first step reaction unit and the second step reaction unit respectively, connect with flange between every grade of main equipment;
(b) four reactor feed gas inlets that link to each other with first step fluidized-bed main equipment barrel in the first step reaction unit are respectively a propylene inlet, a gas inlet, a nitrogen inlet and a steam entry;
(c) preheating section in the reactor feed gas ingress;
(d) gas distributor that is arranged on the gas distributor on preheating section top and is arranged on respective fluidized beds main equipment bottom, gas distributor links to each other with the barrel of fluidized-bed main equipment;
(e) expanding reach that is arranged on behind the first step reaction unit, the inlet of this expanding reach links to each other with the fluidized-bed main equipment of the first step reaction unit, and one be arranged on second expanding reach of step behind the reaction unit, the fluidized-bed main equipment of this expanding reach and the second step reaction links to each other, and is connected with flange between expanding reach and the main equipment;
(f) gas inlet, the first step reaction back that is arranged on first fluidized-bed main equipment bottom of the second step reaction unit, this inlet links to each other with the outlet of the expanding reach of the first step reaction, and first fluidized-bed main equipment bottom of the second step reaction unit also has an air unstripped gas inlet;
(g) pneumatic outlet that is arranged on the expanding reach top of the second step reaction unit.
2, a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation according to claim 1 is characterized in that, described multistage fluidized bed is to be combined in series by a plurality of fluidized-bed main equipments.
3, a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation according to claim 1 is characterized in that, described gas distributor is any in variable mass drift tube type sparger, multiaperture-type sparger, the float-valve type sparger.
4, a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation according to claim 3, it is characterized in that, the pressure drop of described gas distributor is 20%～35% of a beds total pressure drop, and the ratio that is not more than the bubble of 4mm by diameter in the incipient bubble of its generation is 75%～90%.
5, a kind of multistage fluidized bed reactor for preparing propenoic acid from propene oxidation according to claim 1, it is characterized in that, described expanding reach separation efficiency can reach more than 98.0% by the design of its diameter, the minimum catalyst particle size that reclaims is 4 μ m, the fluidized-bed main equipment upper extension section of the first step reaction can be avoided the catalyst mix of one, two two-step reactions, the liquid-phase product that the fluidized-bed main equipment upper extension section of second step reaction can avoid the finely grained catalyst contaminate subsequent to reclaim.
6, a kind of described multistage fluidized bed reactor propylene oxidation of claim 1 that utilizes prepares method for producing acrylic acid, it is characterized in that this preparation method comprises the steps:
(1) fluidized-bed main equipments at different levels is linked to each other; Gas inlet, gas distributor, expanding reach link to each other with the fluidized-bed main equipment successively; Fluidized-bed main equipment pneumatic outlet links to each other with expanding reach, constitutes complete multistage fluidized bed reactor;
(2) catalyzer is respectively charged in the fluidized-bed main equipments at different levels of the first step reaction unit and the second step reaction unit, be deposited in the zone of gas distributor top in the fluidized-bed main equipments at different levels, form the catalyzer emulsion zone, the static loading height of catalyzer is 1～2 times of fluidized-bed main equipment diameter;
(3) by gas inlet and nitrogen inlet difference bubbling air and nitrogen, make the catalyzer in the fluidized-bed main equipment be in fluidized state, and heat the main equipment of each step reaction with tile, make that catalyzer emulsion zone temperature reaches 300～320 ℃ in the first step reaction unit; Catalyzer emulsion zone temperature reaches 200～220 ℃ in the second step reaction unit;
(4) by propylene with steam entry feeds propylene respectively and water vapour reacts;
(4.1) with the temperature of catalyzer emulsion zone in every grade of fluidized-bed main equipment of temperature control control the first step reaction unit at 330～375 ℃; The mol ratio of oxygen and propylene is 1.3～2.0 in the air; The mol ratio of water vapour and propylene is 0～3.5; Reactor feed gas cumulative volume air speed is 400～600Lh
-1Kg
-1, propylene cumulative volume air speed is 15～60Lh
-1Kg
-1With nitrogen adjustments of gas flow, make operating gas velocity actual in the fluidized-bed main equipments at different levels reach 0.03～0.05m/s;
(4.2) simultaneously, with the temperature of catalyzer emulsion zone in every grade of fluidized-bed main equipment of second step of temperature control control reaction unit at 270～320 ℃; Gas inlet in the fluidized-bed main equipment of second step reaction continues bubbling air, increases air flow quantity in the reaction of two steps when the gas outlet oxygen content that detects the reaction of second step is lower than 3%;
(5) the part catalyzer in the catalyzer emulsion zone is carried into fluidized-bed main equipment top by air-flow in the last step fluidized-bed main equipment of the first step reaction unit, gaseous product and catalyzer are through the expanding reach after separating, gaseous product goes out the first step reaction back gas inlet of fluidized-bed main equipment bottom first fluidized-bed main equipment that is arranged on the second step reaction unit and enters the second step reaction unit fluidized-bed main equipment, and catalyzer returns the emulsion zone of catalyzer in the last step fluidized-bed main equipment; Part catalyzer in the last step fluidized-bed main equipment of the second step reaction unit in the catalyzer emulsion zone is carried into fluidized-bed main equipment top by air-flow, gaseous product and catalyzer are through the expanding reach after separating, gaseous product goes out the fluidized-bed main equipment, catalyzer returns the emulsion zone of catalyzer in the last step fluidized-bed main equipment, and wherein gaseous product obtains purpose product vinylformic acid through follow-up absorption and rectifying.
7, a kind of described multistage fluidized bed reactor propylene oxidation of claim 1 that utilizes according to claim 6 prepares method for producing acrylic acid, it is characterized in that the catalyzer that adds in the first step reaction unit is Mo-Bi/SiO
2, particle diameter is 0.08～0.12mm, specific surface area is 8～13m
2/ g; The catalyzer that adds in the second step reaction unit is Mo-V/SiO
2, particle diameter is 0.08～0.12mm, specific surface area is 4～8m
2/ g.
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| EP4038077B1 (en) * | 2019-10-01 | 2023-05-31 | Dow Silicones Corporation | Thermal condensation reactor |
| CN111514827B (en) * | 2020-04-26 | 2022-04-01 | 太原科技大学 | Processing device and processing method for preparing methane from synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6441227B1 (en) * | 2000-06-23 | 2002-08-27 | Saudi Basic Industries Corporation | Two stage process for the production of unsaturated carboxylic acids by oxidation of lower unsaturated hydrocarbons |
| WO2006072682A1 (en) * | 2004-12-30 | 2006-07-13 | Arkema France | Method of preparing acrylic acid from propane in the absence of water vapour |
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| US6441227B1 (en) * | 2000-06-23 | 2002-08-27 | Saudi Basic Industries Corporation | Two stage process for the production of unsaturated carboxylic acids by oxidation of lower unsaturated hydrocarbons |
| WO2006072682A1 (en) * | 2004-12-30 | 2006-07-13 | Arkema France | Method of preparing acrylic acid from propane in the absence of water vapour |
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