CN105435805B - Catalyst, with the Catalyst Production acrylic acid and reaction system - Google Patents
Catalyst, with the Catalyst Production acrylic acid and reaction system Download PDFInfo
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- CN105435805B CN105435805B CN201410406781.4A CN201410406781A CN105435805B CN 105435805 B CN105435805 B CN 105435805B CN 201410406781 A CN201410406781 A CN 201410406781A CN 105435805 B CN105435805 B CN 105435805B
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Abstract
Disclose a kind of carbon monoxide-olefin polymeric, with the Catalyst Production acrylic acid and reaction system.The carbon monoxide-olefin polymeric includes the first catalyst (Mo12BibFecCodNieXfYgOh) and the second catalyst (Mo12VbCucWdXeYfOg.The reaction system by reaction zone with isolate and purify district's groups into；The area that isolates and purifies is made up of acrylic acid absorption and separation section (100) and acrylic acid rectifying section (200)；The reaction zone outlet is connected with the bottom gas inlet (203) of the acrylic acid absorption and separation section (100), and the outlet at bottom (105) of the acrylic acid absorption and separation section (100) is connected with the upper entrance (106) of acrylic acid rectifying section (200).
Description
Technical field
The present invention relates to a kind of catalyst for fitting through PROPENE IN GAS PHASE OXIDATION method low energy consumption production acrylic acid, the catalyst
It is especially suitable for low water ratio method for oxidation.The invention further relates to use the Catalyst Production acrylic acid and device.
Background technology
Acrylic acid is important organic chemical industry's intermediate, and extensive purposes is suffered from many fields.The industry of acrylic acid
Production method is propylene gas phase two-step penetration method, i.e. propylene two-step oxidation in the system that oxygen, nitrogen and vapor form is given birth to
Into acrylic acid, the acrylic acid gas phase mixture of generation is reacted, by refining spearation system, obtains acrylic products.
The conventional separation method of prior art mainly includes three kinds of different technology paths：Solvent absorption distillation technology, water
Absorb azeotropic distillation technology and water absorbs extraction and distillation technology：
The advantages of solvent absorption distillation technology is that flow is short, energy consumption is low；Shortcoming is that acrylic acid need to be inhaled using solvent
Receive, operation temperature height, acrylic acid easily polymerize, and the cycle of operation is short.In Chinese patent CN1165808A, diphenyl ether and biphenyl are used
Mixture as absorbent absorbing propenoic acid, then carry out rectifying and isolate purer acrylic acid, this method needs to use
Environmentally harmful solvent, and each step is required for adding expensive polymerization inhibitor prevents acroleic acid polymerization.
The advantages of water absorption azeotropic distillation technology, is shorter for flow, and investment cost is low；Shortcoming is that need to use entrainer energy consumption
Higher, operating cost is high.
The advantages of water absorption extraction and distillation technology is that energy consumption is low, operating cost is low；Shortcoming be the longer investment cost of flow it is high,
It is high using extractant, polymerization inhibitor consumption.
Purification for acrylic acid aqueous solution, consider from Energy Angle, high concentration acrylic acid aqueous solution preferably uses azeotropic smart
Technique removing water is evaporated, and low concentration acrylic acid aqueous solution is more suitable using the technique removing water of extracting rectifying.
Currently used reaction system uses exhaust gas circulation process, is steamed by the circulation of tail gas to reduce the water in unstripped gas
Gas concentration, the acrylic acid concentration of reaction system generation is improved, reduce wastewater treatment capacity.Typically in non-exhaust gas circulation process, water
As absorbent, the concentration of acrylic acid aqueous solution is 45-55wt% after absorption；And in exhaust gas circulation process, equally using water
As absorbent, acrylic acid aqueous solution concentration can be improved to 60%-70wt% after absorption.
For azeotropic distillation technique, Chinese patent CN1865216A proposes a kind of piece-rate system being made up of four towers,
It uses the compositional liquor of ethyl cyclohexane and toluene, ethyl acetate and toluene as entrainer, isolated acrylic acid solution and
Acetic acid solution.
In order to reduce the water content in acrylic acid product, Chinese patent CN101555200A proposes to be added in Distallation systm
Enter drier, such as acetals, keto acetals, halogenation anhydrides, isocyanates etc., these reactive drying agents and water are anti-
Should, finally obtain the acrylic acid product that water content did not grasped 0.2wt%.But the addition of drier adds production cost,
Trouble has been manufactured for follow-up processing.
For extracting rectifying, proposed in Chinese patent CN1241892C by using extractant, such as toluene, acetic acid second
The methods of ester, butyl acetate, ethyl propionate etc., acrylic acid being separated from the aqueous solution, then passing through azeotropic distillation removes
Light component such as water and acetic acid etc..The shortcomings that this method is that stop of the acrylic acid in equipment is longer in extraction process, heated
Acrylic acid is caused to be easier to polymerize and occluding device under state.
Whether azeotropic distillation method or extraction rectifying method, they are required for using organic solvent, and this not only increases
Production cost, is also unfavorable for environmental protection.In addition, prior art uses carries out separating-purifying by four technical process, with
Exemplified by CN 1865216A, as shown in its Fig. 1, it, which isolates and purifies area, includes azeotrope column T1, desacetoxy tower T2, stripper T3 and second
Azeotropic acid rectifying column T4.This four Tower System not only needs high investment and operating cost, and organic entrainer (second therein
Butylcyclohexane and toluene, the compound of ethylpropylene and toluene make entrainer) can also pressure be produced to environment.
Therefore, it is necessary to develop a kind of method for producing propenoic acid, it can low cost (including production cost and Environmental costs)
Acrylic acid product made from ground separation.
The content of the invention
The present invention goal of the invention be to provide a kind of method for producing propenoic acid, it can low cost (including production cost and
Environmental costs) separate obtained product.
The one side that the present invention reaches foregoing invention purpose is to provide a kind of urging for propylene oxidation production acrylic acid
Agent composition, it includes the first catalyst and the second catalyst；
First catalyst is the Mo-Bi composite oxide catalysts for having general formula：
Mo12BibFecCodNieXfYgOh
Wherein, X is selected from least one of W, Sb, Ce, Cr, Mn, La element；
Y is selected from least one of Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba element；
B is 0.5~3；
C is 0.5~3；
D is 3~8；
E is 1~5,
F is 0.05~2,
G is 0.05~1；
H is the numeral that is determined by the oxidation state of above-mentioned each element；
The Mo-Bi composite oxide catalysts are using made from following method：
A) mixture of each element precursor, co-precipitation are provided, and are dried to obtain powder；
B) gross weight meter of final mixture is pressed, adds 5%~40wt% particle diameters as 70~220 μm of Si powder, and into
Type；
C) it is 400h in air speed by obtained article shaped-1To 1200h-1Air in 160~250 DEG C be calcined 15~30
Hour；Then it is calcined 4~20 hours at 450~530 DEG C；
Second catalyst is the Mo-V composite oxide catalysts for having general formula：
Mo12VbCucWdXeYfOg
Wherein X is selected from least one of Nb, Sb, Sr, Ba, Ni element；
Y is selected from least one of La, Ce, Nd, Sm element；
B is 2~6；
C is 0.5~3；
D is 0.5~3；
E is 0.1~4；
F is 0.01~2；
H is the numeral that is determined by the oxidation state of above-mentioned each element；
The Mo-V composite oxide catalysts are as made from following method：
A) mixture of each element precursor is provided, be co-precipitated and dry, obtain powder；
B) gross weight meter of final mixture is pressed, adds the Si powder that 40%~65wt% particle diameters are 70~220 μm, into
Type, obtain article shaped；
C) by the article shaped in the mixed of the ammonia containing 3%~30vol%, 3%~10vol% oxygen and surplus nitrogen
Close in gas and be calcined 4~18 hours in 240~300 DEG C, in the atmosphere that oxygen content is more than 3vol% and surplus nitrogen in 350~
400 DEG C are calcined 3~18 hours.
The another aspect that the present invention reaches foregoing invention purpose is to provide a kind of method for producing acrylic acid, and it includes as follows
Step：
(a) the first and second catalyst of the above-mentioned carbon monoxide-olefin polymeric of the present invention are respectively placed in two conversion zones；
(b) raw mixture containing propylene, oxygen and optional vapor is passed sequentially through the conversion zone, reacted
Mixture, the volume ratio of vapor and propylene is 0-0.8 in the raw mixture：1；
(c) reactant mixture is passed through and isolates and purifies area by what acrylic acid absorption and separation section and acrylic acid rectifying section formed,
Isolated acrylic acid.
Another aspect of the invention be related to it is a kind of aoxidize the reaction system to form acrylic acid for propylene, it by reaction zone and
Isolate and purify district's groups into；
The reaction zone is by concatenating first reactor equipped with one section of catalyst and second equipped with two sections of catalyst anti-
Device is answered to form；
The area that isolates and purifies is made up of the acrylic acid absorption and separation tower and acrylic acid purifying column concatenated；
The second reactor outlet is connected with the entrance of the acrylic acid absorption and separation tower.
Brief description of the drawings
Fig. 1 is the flow chart that the inventive method isolates and purifies area.
Fig. 2 is the flow chart that prior art isolates and purifies area.
Embodiment
In the present invention, term " low water ratio system " refers to that the volume ratio of vapor and propylene is 0-0.8 in reaction system：
1, preferably 0.05-0.7：1, more preferably 0.15-0.65：1, preferably 0.2-0.6：1, preferably 0.25-0.6：1
In the present invention, term " low water ratio catalyst " or " low water ratio carbon monoxide-olefin polymeric " refer to be adapted to the present invention low
Oxidation reaction catalyst or carbon monoxide-olefin polymeric of the water than system.
In the present invention, term " acrylic acid " includes acrylic acid and methacrylic acid, is only preparing acrylic acid process
The middle raw material used is propylene, and it is isobutene to prepare the raw material used during methacrylic acid.The present invention one compared with
In good example, the acrylic acid refers to that chemical formula is CH2=CH-COOH compound.
A.Low water ratio carbon monoxide-olefin polymeric
The present invention provides a kind of carbon monoxide-olefin polymeric for aoxidizing production acrylic acid by propylene in low water ratio system, and it is wrapped
Include the first catalyst and the second catalyst.
1) the first catalyst
First catalyst is the Mo-Bi composite oxide catalysts for having general formula：
Mo12BibFecCodNieXfYgOh
Wherein, X be selected from least one of W, Sb, Ce, Cr, Mn, La element, it is preferably at least one selected from W, Sb,
La element；
Y is to be selected from selected from least one of Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba element, preferably at least one
Na, K, Ca element；
B is 0.5~3, preferably 0.7-2.8, more preferably 0.9-2.5, preferably 1.1-2.0, preferably 1.2-1.8, such as
1.15th, 1.25,1.28,1.69,1.75,1.85 etc.；
C is 0.5~3, preferably 0.8-2.8, more preferably 1.0-2.6, preferably 1.2-2.5, preferably 1.8-2.2, such as
1.4th, 1.6,2.3 etc.；
D is 3~8, preferably 4.0-7.5, more preferably 4.4-7.0, preferably 4.8-6.5, preferably 5.19-5.62, such as
4.9th, 5.0,5.1,5.8,6.2 etc.；
E is 1~5, preferably 1.4-4.5, more preferably 1.6-4.0, preferably 2.0-3.0, preferably 2.3-2.8, such as 2.2,
2.4th, 2.6 etc.；
F is 0.05~2, preferably 0.08-1.9, more preferably 0.1-1.8, preferably 0.2-1.6, preferably 0.3-1.4, such as
0.52nd, 0.86,1.34,0.7,0.9,1.5 etc.；
G is 0.05~1, preferably 0.08-0.9, more preferably 0.10-0.8, preferably 0.13-0.7, preferably 0.13-0.5, example
Such as 0.18,0.25,0.26,0.3,0.4；
H is the numeral that is determined by the oxidation state of above-mentioned each element.
In an example of the present invention, first catalyst is selected from
Mo12Fe1.84Co5.19Ni2.40Bi1.69K0.11Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.48Fe2.03Co5.62Ni2.40Bi1.28K0.12Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12Fe1.88Co5.25Ni2.48Bi1.89K0.18Na0.07Ca0.10Sb0.12La0.86Oh；
Mo12W0.58Fe2.13Co5.42Ni2.30Bi1.30K0.15Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.50Fe1.93Co5.01Ni2.42Bi1.50K0.18Na0.15Ca0.09Sb0.18La0.92Oh；
Mo12Fe1.98Co4.95Ni2.32Bi1.85K0.08Na0.17Ca0.21Sb0.18La0.96Oh；Or its two or more formation
Mixture.
First catalyst (also known as Mo-Bi composite oxide catalysts) of the invention is using made from following method：
A) mixture of each element precursor, co-precipitation are provided, and are dried to obtain powder
In the present invention, term " elemental precursors " refers to the precursor that can form element oxide in composite oxides, and it is logical
It is often the soluble-salt of the element.It is without particular limitation to be suitable for the elemental precursors of the inventive method, can be known in the art
The soluble-salt of the element etc..
It is without particular limitation to be suitable for the coprecipitation method of the present invention, can be any conventional method known in the art,
Such as by adjusting the pH value of mixture solution, oxidation state by changing element etc..
It is without particular limitation to be suitable for the method drying means of the present invention, can be that any of routine of this area is done
Drying method.
B) gross weight meter of final mixture is pressed, adds 5%~40wt% particle diameters as 70~220 μm of Si powder, and into
Type
In the present invention, Si powder plays a part of to dilute thermal conducting agent, and its addition preferably accounts for final mixture gross weight
8-38 weight %, 10-35 weight % are more preferably accounted for, preferably account for 12-32 weight %, preferably 15-30 weight %.
As the particle diameter preferably 70-210 microns of the Si powder of dilution thermal conducting agent, more preferably 70-200 microns, preferably 70-
180 microns, preferably 70-160 microns.
The forming method of first catalyst of the invention is without particular limitation, can be forming method known in the art.
In an example of the present invention, by the gross weight meter of final mixture, 0.01%~10 weight %, preferable 0.1-8 weights are added
% is measured, more preferable 0.5-6 weight %, preferably 0.8-4 weight % binding agent are simultaneously well mixed, coated on spherical, cylindrical, three leaves
On the solid or hollow inert carriers such as careless shape, bunge bedstraw herb shape, gear shape, or it is directly formed to above-mentioned given shape.
C) it is 400h in air speed by obtained article shaped-1To 1200h-1Air in 160~250 DEG C be calcined 15~30
Hour；Then it is calcined 4~20 hours at 450~530 DEG C
Present invention article shaped obtained above 450h more fortunately-1To 1000h-1Air in, more preferably in 500h-1To 950h-1
Air in, preferably in 550h-1To 900h-1Air in, preferably in 600h-1To 850h-1Air in be calcined.
The temperature of roasting preferably 160~240 DEG C, more preferably 160-220 DEG C, preferably 170-210 DEG C.
The preferably 18-28 hours time of roasting, more preferably 20-26 hours, preferably 22-24 hours.
The manufacture method of first catalyst of the invention also includes again existing the catalyst blank for being calcined to obtain under above-mentioned condition
It is calcined at higher temperature in the air of identical air speed (or high-temperature roasting).
The temperature of the high-temperature roasting preferably 460~520 DEG C, more preferably 470-510 DEG C, preferably 480-500 DEG C.
The preferably 6-18 hours time of the high-temperature roasting, more preferably 8-16 hours, preferably 10-14 hours, preferably 11-13
Hour.
In an example of the present invention, the manufacture method of first catalyst comprises the following steps：By appropriate molybdenum
Sour ammonium, potassium nitrate, sodium nitrate, calcium acetate and antimony oxide are dissolved in water to obtain solution (1)；By appropriate cobalt nitrate, nickel nitrate, nitre
Sour iron and lanthanum nitrate are dissolved in water, and add nitric acid and bismuth nitrate obtains solution (2)；Solution (2) is instilled into solution (1) to be starched
Shape liquid.Will the pulpous state liquid dry after add Si powder, graphite and silica, mixing, beat sheetmolding for required shape (such as
Hollow cylindrical) particle.Shaped granule is in 400h-1To 1200h-1Roasted in the air of air speed at a temperature of 160~250 DEG C
Burn 15~30 hours, then be calcined 4~20 hours at 450~530 DEG C, obtain the first required catalyst.
In another example of the present invention, the manufacture method of first catalyst include by ammonium molybdate, ammonium paratungstate,
Potassium nitrate, sodium nitrate, calcium acetate and antimony oxide are dissolved in water to obtain solution (1)；Nitric acid, bismuth nitrate stirring and dissolving are obtained into solution
(2)；Cobalt nitrate, nickel nitrate, ferric nitrate and lanthanum nitrate are dissolved in water to obtain solution (3)；Solution (2) is instilled into solution (1), then
Solution (3) is instilled to the mixed liquor of solution (1) and solution (2), hydrogen peroxide is added, the pulpous state liquid of stirring to obtain, is subsequently dried,
Obtain catalyst precarsor.Si powder, graphite and silica are added into the catalyst precarsor, mixing, it is required shape to beat sheetmolding
Shape (such as hollow cylindrical) particle.Shaped granule is in 400h-1To 1200h-1In 160~250 DEG C of temperature in the air of air speed
Lower roasting 15~30 hours, then be calcined 4~20 hours at 450~530 DEG C, obtain the first required catalyst.
2) the second catalyst
Second catalyst of the invention is the Mo-V composite oxide catalysts for having general formula：
Mo12VbCucWdXeYfOg
Wherein X be selected from least one of Nb, Sb, Sr, Ba, Ni element, it is preferably at least a kind of selected from Sb, Sr, Ba,
Ni element；
Y is selected from least one of La, Ce, Nd, Sm element, preferably La and/or Ce, more preferably La；
B is 2~6, preferably 2.2-5.6, more preferably 2.4-5.4, preferably 2.6-5.2, preferably 3-4.5, such as 2.80,
3.05th, 3.75,3.95,4.20 etc.；
C is 0.5~3, preferably 0.6-2.8, more preferably 0.7-2.6, preferably 0.8-2.4, preferably 0.9-2.0, for example,
0.85th, 0.98,1.22,1.35,1.45 etc.；
D is 0.5~3, preferably 0.7-2.8, more preferably 0.8-2.6, preferably 0.9-2.4, preferably 1.0-2.2, such as
0.98th, 1.12,1.25,1.30 etc.；
E is 0.1~4, preferably 0.1-3.7, more preferably 0.1-3.2, preferably 0.1-3.0, preferably 0.1-2.8, such as
0.23rd, 0.58,1.08,1.5,2.05,2.16,2.18,2.30,2.35 etc.；
F is 0.01~2, preferably 0.02~1.8, more preferably 0.03~1.6, preferably 0.04~1.4, preferably 0.05-
1.2, such as 0.07,0.09,0.25,0.58,1.12 etc.；
H is the numeral that is determined by the oxidation state of above-mentioned each element.
In an example of the present invention, second catalyst is selected from
Mo12V3.05W1.12Cu0.98Sb1.71Sr0.25Ni0.13Ba0.09La0.05Oh；
Mo12V3.75W1.12Cu1.22Sb1.86Sr0.30La0.05Oh；
Mo12V3.25W1.02Cu0.88Sb1.21Sr0.15Ni0.23Ba0.07La0.06Oh；
Mo12V2.95W1.18Cu1.08Sb1.75Sr0.20Ni0.20Ba0.08La0.06Oh；
Mo12V3.85W1.02Cu1.25Sb0.89Sr0.35La0.06Oh；；
Mo12V3.25W1.22Cu1.02Sb1.76Sr0.28La0.07Oh；Or the mixture of its two or more formation.
Second catalyst (also known as Mo-V composite oxide catalysts) of the invention is as made from following method：
A) mixture of elemental precursors is provided, be co-precipitated and dry, obtain powder
It is suitable for that the elemental precursors of the inventive method are without particular limitation, can is the solvable of the element known in the art
Property salt etc..
It is without particular limitation to be suitable for the coprecipitation method of the present invention, can be any conventional method known in the art,
Such as by adjusting the pH value of mixture solution, oxidation state by changing element etc..
It is without particular limitation to be suitable for the method drying means of the present invention, can be that any of routine of this area is done
Drying method.
B) gross weight meter of final mixture is pressed, adds the Si powder that 40%~65wt% particle diameters are 70~220 μm, into
Type, obtain article shaped
In the present invention, Si powder plays a part of to dilute thermal conducting agent, and its addition preferably accounts for final mixture gross weight
42-62 weight %, 45-60 weight % are more preferably accounted for, preferably account for 48-58 weight %, preferably 50-55 weight %.
As the particle diameter preferably 70-210 microns of the Si powder of dilution thermal conducting agent, more preferably 70-200 microns, preferably 70-
180 microns, preferably 70-160 microns.
The forming method of second catalyst of the invention is without particular limitation, can be forming method known in the art.
In an example of the present invention, by the gross weight meter of final mixture, 0.01%~10 weight %, preferable 0.1-8 weights are added
% is measured, more preferable 0.5-6 weight %, preferably 0.8-4 weight % binding agent are simultaneously well mixed, coated on spherical, cylindrical, three leaves
On the solid or hollow inert carriers such as careless shape, bunge bedstraw herb shape, gear shape, or it is directly formed to above-mentioned given shape.
C) by the article shaped in the mixed of the ammonia containing 3%~30vol%, 3%~10vol% oxygen and surplus nitrogen
Close in gas and be calcined 4~18 hours for the first time in 240~300 DEG C, in the atmosphere that oxygen content is more than 3vol% and surplus nitrogen
In 350~400 DEG C second be calcined 3~18 hours
The mixed gas preferably ammonia containing 5%~25vol%, the 4%~9vol% that are calcined for first time oxygen
With surplus nitrogen；The more preferably ammonia containing 8%~22vol%, 5%~8vol% oxygen and surplus nitrogen；Preferably contain 10%
~20vol% ammonia, 6%~7vol% oxygen and surplus nitrogen.
Preferably 250-290 DEG C, more preferably 260-280 DEG C of temperature being calcined for first time.
Preferably 4-16 hours time being calcined for first time, more preferably 5-14 hours, preferably 6-12 hours, preferably 7-
10 hours.
It is nitrogen to be adapted to second of preferable oxygen content of atmosphere being calcined to be more than 5vol% and surplus, and more preferable oxygen content is big
It is nitrogen in 6vol% and surplus, it is nitrogen that suitable oxygen content, which is more than 7vol% and surplus, and preferably oxygen content is more than 8vol%
And surplus is nitrogen.In an example of the present invention, the atmosphere of second of roasting is air.
Preferably 360-390 DEG C, more preferably 370-380 DEG C of the temperature of second of roasting.
Preferably 4-16 hours time of second of roasting, more preferably 5-15 hours, preferably 6-12 hours, preferably 7-
10 hours.
In an example of the present invention, the manufacture method of second catalyst, which is included in, aoxidizes ammonium paramolybdate and three
Two antimony are dispersed with stirring in water, are dried and are calcined to obtain oxide A；By ammonium paramolybdate, ammonium metatungstate, ammonium metavanadate, strontium nitrate, nitre
Sour barium and antimony oxide are dissolved in water to obtain solution (1)；Copper nitrate, nickel nitrate and lanthanum nitrate are dissolved in water to obtain solution
(2)；Solution (2) and oxide A are added in solution (1), obtained mixed liquor obtains catalyst precarsor after drying.To the catalysis
Si powder and graphite are added in agent precursor, beats sheetmolding into shaping (such as hollow cylindrical) particle.By shaped granule containing 3%
Roasted for the first time in 240~300 DEG C in the mixed gas of~30vol% ammonia, 3%~10vol% oxygen and surplus nitrogen
Burn 4~18 hours, it is small in 350~400 DEG C of second of roastings 3~18 in the atmosphere that oxygen content is more than 3vol% and surplus nitrogen
When, obtain catalyst.
In another example of the present invention, the manufacture method of second catalyst includes aoxidizing ammonium paramolybdate and three
Two antimony are dispersed in water, and are dried and are calcined to obtain oxide A；By ammonium paramolybdate, ammonium metatungstate, ammonium metavanadate, strontium nitrate and three oxygen
Change two antimony and be dissolved in water to obtain solution (1)；Copper nitrate and lanthanum nitrate are dissolved in water to obtain solution (2)；Added into solution (1)
Solution (2) and oxide A, Si powder and graphite are added after drying, beat sheetmolding into shaping (such as hollow cylindrical) particle.Will
Shaped granule is in the mixed gas of the ammonia containing 3%~30vol%, 3%~10vol% oxygen and surplus nitrogen in 240
~300 DEG C of roasting 4~18 hours for the first time, in 350~400 DEG C the in the atmosphere that oxygen content is more than 3vol% and surplus nitrogen
After baking 3~18 hours, obtains catalyst.
Inventive catalyst composition applies to the high-performance composite oxide of low water ratio technique, and it steams in relatively low water
Can be corresponding acrylic acid product by propylene Efficient Conversion, and there is high yield under gas concentration.Catalyst combination of the present invention
The first catalyst (or Mo-Bi O composite metallic oxide catalysts) in thing can aoxidize propylene generation methacrylaldehyde, the second catalysis
Obtained acrolein oxidation can be generated acrylic acid by agent (or Mo-V O composite metallic oxide catalysts).
Inventive catalyst composition is applied to low water ratio system, and water vapor concentration is can be with as little as 0% in reaction system；
O2Mol ratio with propylene is 1~10：1；N2Mol ratio with propylene is 1~10：1；Propylene relative to catalyst volume space velocity
For 90~200h-1。
The amount ratio of first catalyst and the second catalyst described in inventive catalyst composition (or weight ratio) nothing
Special limitation, can be the arbitrary proportion for being adapted to oxidation reaction.One of ordinary skill in the art is anti-according to specific oxidation
Should require that specific ratio can be readily determined.In an example of the present invention, first catalyst and the second catalyst
Weight ratio be 10：1-1：10, preferably 8：1-1：8, preferably 5：1-1：5, more preferably 3：1-1：3, best 2：1-1：2, preferably
1：1.
B.Method for producing acrylic acid
Acrylic acid manufacture of the present invention includes：
(a) the first and second catalyst of inventive catalyst composition are respectively placed in two conversion zones
The catalyst of propylene is aoxidized into generation methacrylaldehyde catalyst and acrolein oxidation generation acrylic acid is placed in two strings
The series-mounting of the method for the conversion zone connect and two conversion zones in itself is without particular limitation, and it can be any normal of this area
Rule method, as long as substituting the conventional catalyst composition of this area with inventive catalyst composition.
(b) raw mixture containing propylene, oxygen and optional vapor is passed sequentially through the conversion zone, reacted
Mixture, the volume ratio of vapor and propylene is 0-0.8 in the raw mixture：1
Raw mixture containing propylene, oxygen and vapor is carried out catalysis oxidation prepare the reaction method of acrylic acid without
Special limitation, it is well-known in the art.But raw mixture of the present invention uses low water ratio system, i.e. raw material mixes
The volume ratio of vapor and propylene is 0-0.8 in thing：1, preferably 0.05-0.7：1, more preferably 0.15-0.65：1, preferably 0.2-
0.6：1, preferably 0.25-0.6：1.
Generally, the gas phase reaction mixture that above-mentioned reactions steps obtain mainly contains nitrogen N2, oxycarbide COx, oxygen O2, third
Alkene, acrylic acid, acetic acid, steam and maleic acid.
In an example of the present invention, the content of acrylic acid accounts for 13-14mol%, water vapour in gas phase reaction mixture
Account for 4-7.5mol%.
Because the inventive method uses low water ratio carbon monoxide-olefin polymeric, therefore above-mentioned oxidation reaction can be in low water vapour content
Lower progress, as a result obtained reactant mixture there is higher acrylic acid concentration.The acrylic acid reactant mixture of this high concentration
Can be isolated and purified by such area that isolates and purifies, i.e., it only by acrylic acid absorption and separation section and acrylic acid rectifying section this two
Individual post processing section composition, obtained acrylic acid purity and yield are separated with what prior art used by what four post processing sections formed
Zone purification is suitable.As a result equipment investment and operating cost are greatly simplified.
(c) reactant mixture is passed through and isolates and purifies area by what acrylic acid absorption and separation section and acrylic acid rectifying section formed,
Isolated acrylic acid
The inventive method includes reacting the obtained feeding of the gas phase mixture containing acrylic acid product by acrylic acid absorption point
Area is isolated and purified from what section and acrylic acid rectifying section formed, this isolates and purifies coupling of the area by absorption process and purification process：
In acrylic acid absorption and separation section, made by the use of the acrylic acid solution for containing acetic acid as quenching medium, aqueous acetic acid
The absorption of acrylic acid is carried out for absorbent, absorbing liquid is sent into follow-up acrylic acid rectifying section.Due to the absorption refining section only
Part steam in condensation reaction mixture, therefore the concentration of acrylic acid can reach 80wt% or higher in its liquid phase mixture；
In acrylic acid rectifying section, the absorbing liquid containing 80wt% or higher acrylic acid is separated, obtain acrylic acid product and
Acetic acid mixed solution, the acetic acid mixed solution are recycled back to the acrylic acid absorption and separation section as cooling agent and absorption
Agent.
The present invention isolates and purifies area and is only made up of acrylic acid absorption and separation section and acrylic acid rectifying section, and its is isolated
Purity of acrylic acid product is higher than 99.0wt%, preferably higher than 99.5wt%, and the quantity of steam that acrylic acid per ton is consumed is less than 1.5
Ton, preferably below 1.1 tons.And the production system of existing non-low water ratio catalyst needs point using four post processing section compositions
From zone purification, the quantity of steam that its acrylic acid per ton is consumed is at 2.4 tons or so.
C. the reaction system to form acrylic acid is aoxidized for propylene
Propylene of the present invention aoxidize to be formed acrylic acid reaction system be by reaction zone with isolate and purify district's groups into.
I) reaction zone
The reaction zone be this area it is conventional aoxidize the reactor to form acrylic acid for propylene, it is only therein to urge
Agent is replaced into low water ratio carbon monoxide-olefin polymeric of the present invention.In an example of the present invention, the reaction zone is by the dress that concatenates
It is made up of the first reactor of the first catalyst and the second reactor equipped with the second catalyst.In first reactor inner propene quilt
Gaseous oxidation generates methacrylaldehyde and acrylic acid, product enter second reactor, is further oxided in the reactor inner propene aldehyde
Generate acrylic acid.
The running temperature of first and second reactor is without particular limitation, can be any conventional temperature of this area
Degree.In an example of the present invention, the running temperature of the first reactor is 300-400 DEG C, preferably 310-360 DEG C；
The running temperature of the second reactor is 200-300 DEG C, preferably 210-290 DEG C, more preferably 230-280 DEG C.
In an example of the present invention, raw mixture is passed through reactor of the present invention, the raw mixture reclaimed water
The volume ratio of steam and propylene is 0-0.8：1, preferably 0.05-0.7：1, more preferably 0.15-0.65：1, preferably 0.2-0.6：1,
It is preferred that 0.25-0.6：1.The mol ratio of oxygen and the propylene mixed gas is 1-10:1, preferably 1-8：1, preferably 1-5：1.
The mol ratio of nitrogen and the propylene mixed gas is 1-10:1, preferably 1-8：1, preferably 1-5：1.In the reality of the present invention
In example, in the porch supplemental oxygen of second reactor and the mixed gas of propylene.Oxygen and the propylene mixed gas is rubbed
Your ratio is 1-5:1, preferably 1-4：1, preferably 1-3：1.
Generally, the gas phase reaction mixture that above-mentioned reactions steps obtain mainly contains nitrogen N2, oxycarbide COx, oxygen O2, third
Alkene, acrylic acid, acetic acid, steam and maleic acid.
In an example of the present invention, the content of acrylic acid accounts for 13-14mol%, water vapour in gas phase reaction mixture
Account for 4-7.5mol%.
Ii area) is isolated and purified
The existing area that isolates and purifies generally is made up of four processing sections (or kettle) concatenated.As shown in Fig. 2 this four processing
Section includes：
Absorption section：Reaction zone exit reactant mixture is sent into absorption tower 10, and absorbent uses the top of dehydrating tower 20
Efflux, acrylic acid, acetic acid, maleic acid in reacting gas etc. obtains propylene sour water by the tower reactor that absorption is got off on absorption tower 10
Solution.Using exhaust gas circulation process, the wherein part of 10 overhead gas of absorption tower 11 12 returns to reaction zone, the conduct of another part 13
Waste gas is handled to emission-control equipment.
It is dehydrated workshop section：The tower reactor acrylic acid aqueous solution 14 on absorption tower 10 is sent to acrylic acid dehydrating tower 20, acrylic acid dehydration
Tower 20 makees entrainer using toluene, and entrainer toluene used in dehydrating tower 20 adds from tower top, toluene and water, toluene and acetic acid
Steamed in the form of azeotropic mixture from tower top.The mixture for forming toluene, water, acetic acid is condensed through overhead condenser 21.Due to toluene
It is immiscible with water, two-phase, oil phase (toluene phase) and water are formed in quantizer, oil phase toluene returns to the tower top of dehydrating tower 20 as altogether
Agent is boiled, absorbent of a part of water as absorption tower in aqueous phase, remaining water discharge system progress burning disposal.
De- acetic acid workshop section：The kettle liquid 22 of dehydrating tower 20 mainly contains acrylic acid, toluene and acetic acid, and it is admitted to acetic acid separated
Tower 30, here, low boiling toluene and acetic acid and part acrylic acid steam from tower top, wherein acetic acid and toluene are with azeotropic mixture
What form steamed, the liquid of top of the tower 31 of de- acetic acid tower 30 mainly contains acrylic acid, acetic acid and toluene, and it returns to propylene through pipeline 32
Sour dehydrating tower 20, to reclaim acrylic acid and toluene therein and remove acetic acid therein.
Purify workshop section：The tower bottoms 33 of de- acetic acid tower 30 mainly contains acrylic acid, acrylic acid heavy constituent (predominantly acrylic acid
Dimer), maleic acid etc., the tower bottoms 33 is sent to acrylic acid purifying column 40.The tower top of acrylic acid purifying column 40 obtains purity
For 99.5wt% acrylic products 41.
It is of the present invention isolate and purify area by concatenate acrylic acid absorption and separation section (or kettle) and acrylic acid rectifying section (or
Kettle) composition, the second reactor exports to be connected with the bottom gas inlet of the acrylic acid absorption and separation section, the acrylic acid
The outlet at bottom of absorption and separation section is connected with the upper entrance of acrylic acid rectifying section.
In an example of the present invention, the top of the acrylic acid absorption and separation section is also connected including one with condenser
Gas vent and the liquid inlet that is connected with the condenser, for using after a part of gas condensation in segregation section as absorption
Liquid.
In an example of the present invention, the top exit of the acrylic acid rectifying section and the bottom liquid of the segregation section
Entrance is connected, and the bottom liquid inlet is located at the top of the bottom gas inlet.
Fig. 1 is the flow chart that the present invention isolates and purifies area.As described in Figure 1, the present invention, which isolates and purifies area, is inhaled by acrylic acid
Receive segregation section 100 and acrylic acid rectifying section 200 is formed.Gaseous reaction mixture 300 from reaction zone is from absorption and separation section
100 lower entrances 203 are sent into and flowed up under the driving of pressure, waste liquid 202 from rectifying section 200 (containing acetic acid and
The solution of a small amount of acrylic acid) it is sent into the entrance 204 of the absorption and separation section top of lower entrances 203 along pipeline 202, and to flowing down
It is dynamic and with the counter current contacting of gaseous reaction mixture 300, so as to which most of acrylic acid in gaseous reaction mixture (be boiled under normal pressure
About 141 DEG C of point), part acetic acid (117 DEG C of boiling point under normal pressure) and part steam (100 DEG C of boiling point under normal pressure) be cooled to liquid.
The liquefied gaseous mixture that is not cooled rises to the top of absorption and separation section 100, a part of liquefied mixture from
Outlet 101 effusion after be admitted to condensing unit 102 carry out cooling liquid, obtained liquid be admitted to entrance 103 and 104 be used for pair
Follow-up gaseous reaction mixture is cooled down, absorbed.Unabsorbed gas (such as oxycarbide, acetic acid) is then in absorption and separation section
Top 108 reclaim or empty.
Be in a liquid state after being absorbed acrylic acid in the acrylic acid solution 105 of shape concentration up to 80wt% or higher, it is inhaling
The bottom for receiving segregation section 100 is divided into two strands, and one merges into cooling and absorbed along pipeline 107 and the waste liquid 202 from pipeline 202 is situated between
Matter, another stock are then sent to acrylic acid rectifying section 200 along pipeline 106 and purified.
In an example of the present invention, the acrylic acid purifying column 200 only sets profit reduction and reserving Duan Erwu rectifying sections.Top gaseous phase
The condensed device 210 of material 205 returns to absorber portion 100 through pipeline 202 as coolant (or waste liquid) after condensing and is used as gas cold
But agent.Technical grade acrylic acid can obtain by the side line of acrylic acid rectifying section 200, purity is more than 99.0wt%, and tower reactor obtains purity
About 70.0wt% acrylic acid heavy constituent.
The present invention is carried out by the use of the acrylic acid aqueous solution for containing acetic acid as quenching medium, aqueous acetic acid as absorbent
The absorption of acrylic acid, the acetic acid for reacting generation separate discharge from the tower top of absorption and separation section 100, the distillation point in rectifying section 200
Separate out the acrylic acid of high-purity, while the acrylic acid that obtains after cooling of overhead gas and acetic acid mixed solution return to absorption and separation
Section 100, as cooling agent and absorbent.Due to used be applied to low water ratio technique catalyst and low water vapor concentration it is anti-
Technique is answered, reduces the water content in the acrylic acid gas phase mixture generated in reaction system, while cooling-suction of separating-purifying
Receipts-separation process reclaimed water is recycled, it is not necessary to the water outside supplementary quota, also without using other solvent (extractant, azeotropic
Agent), pollution of the solvent to environment is avoided, has also accomplished non-wastewater discharge, has reduced energy consumption.
The present invention is further described by the following embodiment, but protection domain should not be limited by the examples.
Embodiment 1
Catalyst preparation and oxidation reaction：
(1) prepared by Mo-Bi-O systems O composite metallic oxide catalyst：
3000mL water is heated to 60 DEG C, adds ammonium molybdate 1421.6g, potassium nitrate 7.1g, sodium nitrate 2.6g, calcium acetate
9.6g, antimony oxide 10.1g, stirring and dissolving obtain solution (1), and temperature is maintained at 70 DEG C.
After 1300mL water is heated into 50 DEG C, cobalt nitrate 1013.3g, nickel nitrate 467.3g, ferric nitrate are sequentially added
500.0g, 220.8g lanthanum nitrate, stirring and dissolving, add nitric acid 30mL, bismuth nitrate 550.0g stirring and dissolvings obtain solution (2), temperature
Degree is maintained at 50~70 DEG C.
In the case where 70 DEG C are stirred vigorously, (2) solution is instilled into (1) solution, the pulpous state liquid of acquisition is in 150 DEG C of dry 24h.By most
The gross weight meter of whole mixture, Si powder, 1 weight % average grain diameters that 10 weight % average grain diameters are 210 μm are added thereto
The silica that graphite and 2.0 weight % average grain diameters for 162 μm are 176 μm, mixing, it is external diameter 5mm to beat sheetmolding, internal diameter
2mm, length 3mm hollow cylindrical particles.Preformed catalyst is 900h in air speed-1Air in respectively 180~250 DEG C roasting
18h is burnt, then 8h is calcined at 500 DEG C.
(2) prepared by Mo-V-O systems O composite metallic oxide catalyst：
237.0g ammonium paramolybdates and 99.6g antimony oxides are added in 80 DEG C of 1300mL water, 20h is stirred, at 150 DEG C
Lower dry 10h, roasting 8h obtains oxide A at 200 DEG C.
Added in 80 DEG C of 6000mL water 1562.7g ammonium paramolybdates, 240.8g ammonium metatungstates, 303.1g ammonium metavanadates,
45.1g strontium nitrates, 20.2g barium nitrates, 112.7g antimony oxides, stirring and dissolving obtain solution (1).
200.4g copper nitrates, 32.7g nickel nitrates and 19.8g lanthanum nitrates, stirring and dissolving are added in 60 DEG C of 1200mL water
Obtain solution (2).
Solution (2) and oxide A are added in solution (1) at 60 DEG C, obtained mixed liquor dries 10h at 150 DEG C.Press
The gross weight meter of final mixture, 45.8 weight % average grain diameters are added thereto and are averaged for 172 μm of Si powder and 2 weight %
Particle diameter is 135 μm of graphite, mixing, and it is external diameter 5mm to beat sheetmolding, internal diameter 2mm, length 3mm hollow cylindrical particles.Shaping
Catalyst is calcined 8h in the mixed gas containing 14 volume % ammonias, 8 volume % oxygen and surplus nitrogen in 260 DEG C, then in oxygen
In the gas that content is 18 volume % and surplus is nitrogen 6h is calcined in 375 DEG C.
(3) propylene oxidation reaction：
The mixed gas of propylene, oxygen gas and water and nitrogen is passed through reaction system and carries out third by Catalyst packing in reactor
Ene oxidation reaction, the mol ratio that first reactor propylene/oxygen/water steam/adds nitrogen is 1/1.7/0.6/2.8, and second is anti-
Answer device add oxygen/propylene mol ratio be 0.5.As a result show, first reactor and second reactor temperature are respectively 330 DEG C
With 266 DEG C, acrylic acid yield be 88.7%.
(4) acrylic acid separating-purifying：
As shown in figure 1, reactant mixture 300 is that composition is N at reaction system area2(70.3wt%), COx
(0.34wt%), O2(0.36wt%), propylene (0.1wt%), acrylic acid (13.7wt%), acetic acid (1.0wt%), water
(7.3wt%) and maleic acid (0.1wt%) gaseous mixture containing acrylic acid.By the gaseous mixture 300 from acrylic acid absorption and separation tower
The absorption tower 100 is sent into the bottom 203 of tower 100.Enter after distillate 202 from the top of acrylic acid purifying column 200 is heated and inhale
Receive the bottom of tower 100.
Phegma 101 is prepared in condensing unit 102 first, after phegma acrylic acid content is qualified (<
0.5wt%) use back liquid 104 instead to flow back, reach the purpose of partial condensation.Tower top pressure is controlled by tail gas regulating valve.
By adjusting tower reactor heating amount, control bottom temperature 85 ± 0.5 (DEG C), tower top temperature 67.5 ± 0.5 (DEG C), tower reactor
Acrylic acid content in solution>87.5wt%, acrylic acid content in overhead condensation liquid<0.5wt%.
The tower reactor solution 105 of acrylic acid absorption and separation tower 100 enters acrylic acid purifying column 200, specifically comprises acrylic acid
(87.5wt%), acetic acid (6.3wt%), water (6.0wt%) and maleic acid (0.2wt%), the main function of acrylic acid purifying column 200
It is separation acrylic acid liquid phase mixture, side take-off acrylic acid, tower top is without backflow.Tower reactor discharge rate is controlled in 1.2-
1.3wt%, tower top discharge rate 56.8%, side take-off purity of acrylic acid product is 99.58wt%.
Acrylic acid per ton consumes 1.1 tons of steam.
Embodiment 2
Catalyst preparation and oxidation reaction：
(1) prepared by Mo-Bi-O systems O composite metallic oxide catalyst：
3500mL water is heated to 60 DEG C, adds ammonium molybdate 1421.6g, ammonium paratungstate 83.6g, potassium nitrate 8.3g, nitric acid
Sodium 2.6g, calcium acetate 9.6g, antimony oxide 10.1g, stirring and dissolving obtain solution (1), and temperature is maintained at 70 DEG C.
After 300mL water is heated into 50 DEG C, nitric acid 30mL is added, bismuth nitrate 415.0g stirring and dissolvings obtain solution (2), temperature
It is maintained at 50 DEG C.
After 1200mL water is heated into 50 DEG C, cobalt nitrate 1098.3g, nickel nitrate 467.3g, ferric nitrate are sequentially added
550.0g, 220.8g lanthanum nitrate, stirring and dissolving obtain solution (3), and temperature is maintained at 50 DEG C.
In the case where 70 DEG C are stirred vigorously, (2) solution is instilled into (1) solution, then (3) solution is instilled into (1) solution, is added
300mL hydrogen peroxide, the pulpous state liquid of stirring to obtain is in 150 DEG C of dry 24h.By the gross weight meter of final mixture, add thereto
Enter graphite that Si powder, 2 weight % average grain diameters that 15 weight % average grain diameters are 150 μm are 180 μm and 1.5 weight % are averaged
Particle diameter is 165 μm of silica, mixing, and it is external diameter 5mm to beat sheetmolding, internal diameter 2mm, length 3mm hollow cylindrical particles.Into
Type catalyst is 1400h in air speed-1Air in respectively 180~250 DEG C be calcined 15h, then 490 DEG C be calcined 5h.
(2) prepared by Mo-V-O systems O composite metallic oxide catalyst：
237.0g ammonium paramolybdates and 77.6g antimony oxides stirring 20h are added in 80 DEG C of 1300mL water, at 150 DEG C
Lower dry 10h, roasting 8h obtains oxide A at 200 DEG C.
Added in 80 DEG C of 6000mL water 1562.7g ammonium paramolybdates, 240.8g ammonium metatungstates, 373.1g ammonium metavanadates,
54.1g strontium nitrates, 152.7g antimony oxides, stirring and dissolving obtain solution (1).
250.8g copper nitrates, 19.8g lanthanum nitrates are added in 60 DEG C of 1200mL water, stirring and dissolving obtains solution (2)；60
Solution (2) and oxide A are added at DEG C in solution (1), obtained mixed liquor dries 10h at 150 DEG C.By final mixture
Gross weight meter, the Si powder that 52wt% average grain diameters are 175 μm and the graphite that 2wt% average grain diameters are 193 μm are added thereto,
Mixing, it is external diameter 5mm to beat sheetmolding, internal diameter 2mm, length 3mm hollow cylindrical particles.Preformed catalyst is containing 20 volume %
8h are calcined in the mixed gas of ammonia, 5 volume % oxygen and surplus nitrogen in 260 DEG C, then in oxygen content are 14 volume % and remaining
Measure in the gas of nitrogen and be calcined 6h in 390 DEG C.
(3) propylene oxidation reaction：
The mixed gas of propylene, oxygen gas and water and nitrogen is passed through reaction system and carries out third by Catalyst packing in reactor
Ene oxidation reaction, the mol ratio that first reactor propylene/oxygen/water steam/adds nitrogen are 1/1.7/0/3.4, and second reacts
The mol ratio that device adds oxygen/propylene is 0.5.As a result show, first reactor and second reactor temperature be respectively 332 DEG C and
270 DEG C, acrylic acid yield is 88.3%.
(4) acrylic acid separation and purification：
As shown in figure 1, it is N that reaction zone exit reactant mixture 300, which is composition,2(73.7wt%), COx
(0.33wt%), O2(0.35wt%), propylene (0.1wt%), acrylic acid (13.5wt%), acetic acid (1.0wt%), water
(4.3wt%) and maleic acid (0.1wt%) gaseous mixture containing acrylic acid, the gaseous mixture 300 is absorbed from tower bottom acrylic acid
The absorption tower is sent into the bottom of knockout tower 100.Enter after distillate 201 from the top of acrylic acid purifying column 200 is heated and absorb
The bottom of tower 100.
Phegma 101 is prepared in condensing unit 102 first, after phegma acrylic acid content is qualified
(＜ 0.5wt%) uses phegma backflow instead, reaches the purpose of partial condensation.Tower top pressure is controlled by tail gas regulating valve.
By adjusting tower reactor heating amount, control bottom temperature 85 ± 0.5 (DEG C), tower top temperature 67.5 ± 0.5 (DEG C), tower reactor
Acrylic acid content in solution>87.5wt%, acrylic acid content in overhead condensation liquid<0.5wt%.
The tower reactor solution of acrylic acid absorption and separation tower enters acrylic acid purifying column, specifically comprises acrylic acid
(87.5wt%), acetic acid (6.3wt%), water (6.0wt%) and maleic acid (0.2wt%), acrylic acid purifying column main function are
Acrylic acid liquid phase mixture, side take-off acrylic acid are separated, tower top is shown in Fig. 1 without backflow, flow.Tower reactor discharge rate is controlled in 1.2-
1.3wt%, side line discharge rate are in 42wt%, tower top discharge rate 56.8%, side take-off purity of acrylic acid product
99.58wt%.
Acrylic acid per ton consumes 1.1 tons of steam.
Comparative example 1
Catalyst preparation and oxidation reaction：
(1) prepared by Mo-Bi-O systems O composite metallic oxide catalyst：
Catalyst preparation process is 50h in air speed with embodiment 1, simply preformed catalyst-1Air in 500 DEG C roasting
8h。
(2) prepared by Mo-V-O systems O composite metallic oxide catalyst：
Catalysis preparation process is calcined 6h at 375 DEG C in atmosphere with embodiment 1, simply preformed catalyst.
(3) propylene oxidation reaction：
As a result oxidation reaction condition is shown, first reactor and second reactor temperature are respectively 343 DEG C with embodiment 1
With 278 DEG C, acrylic acid yield be 87.0%.
From experiment above result, if carrying out aoxidizing instead under low-water ratio conditions using non-low water ratio catalyst
Should, then the yield of acrylic acid, which has, is decreased obviously.
Comparative example 2
(1) catalyst preparation and oxidation reaction：
Catalyst preparation is with comparative example 1, and simply oxidation reaction condition is different, and first reactor propylene/oxygen/water steam/
The mol ratio for adding nitrogen is 1/1.6/1.0/2.4, and the mol ratio that second reactor adds oxygen/propylene is 0.5, reaction temperature
Respectively 332 DEG C and 266 DEG C, acrylic acid yield is 88.3%.
(2) acrylic acid separation and purification purifies：
As shown in Fig. 2 it is N that reaction zone exit reactant mixture 300, which is composition,2(68.9wt%), COx (2.4wt%),
O2(3.7wt%), propylene (0.2wt%), acrylic acid (14.0wt%), acetic acid (0.4wt%), water (8.9wt%) and maleic acid
The gaseous mixture containing acrylic acid of (0.01wt%), the gaseous mixture is sent into absorption tower 10, absorbent uses the top of dehydrating tower 20
Efflux, acrylic acid, acetic acid, maleic acid in reacting gas etc. obtains 51.5wt% by the tower reactor that absorption is got off on absorption tower 10
Acrylic acid aqueous solution.
Using exhaust gas circulation process, the wherein part of 10 overhead gas of absorption tower 11 12 returns to reaction zone, another part 13
As waste gas to emission-control equipment processing.The tower reactor acrylic acid aqueous solution 14 on absorption tower 10 is sent to acrylic acid dehydrating tower 20,
Acrylic acid dehydrating tower 20 makees entrainer using toluene, and entrainer toluene used in dehydrating tower 20 adds from tower top, toluene and water,
Toluene and acetic acid are steamed in the form of azeotropic mixture from tower top.The mixing for forming toluene, water, acetic acid is condensed through overhead condenser 21
Thing.Because toluene and water are immiscible, two-phase, oil phase (toluene phase) and water are formed in quantizer, oil phase toluene returns to dehydrating tower
As entrainer, absorbent of a part of water as absorption tower in aqueous phase, remaining water discharge system is carried out at burning 20 tower tops
Reason.
The kettle liquid 22 of dehydrating tower 20 mainly contains acrylic acid (70.0wt%), toluene (24.6wt%) and acetic acid
(4.5wt%), it is admitted to acetic acid separated tower 30, here, low boiling toluene and acetic acid and part acrylic acid steam from tower top,
Wherein acetic acid and toluene are steamed in the form of azeotropic mixture, and the liquid of top of the tower 31 of de- acetic acid tower 30 mainly contains acrylic acid, acetic acid
And toluene, it returns to acrylic acid dehydrating tower 20 through pipeline 32, to reclaim acrylic acid and toluene therein and remove vinegar therein
Acid.The tower bottoms 33 of de- acetic acid tower 30 mainly contains acrylic acid, acrylic acid heavy constituent (predominantly acrylic acid dimer), maleic acid
Deng the tower bottoms 33 is sent to acrylic acid purifying column 40.The tower top of acrylic acid purifying column 40 obtains third that purity is 99.5wt%
Olefin(e) acid product 41.
Acrylic acid per ton consumes 2.4 tons of steam.
Comparative example 3
(1) catalyst preparation and oxidation reaction：
Catalyst preparation is with comparative example 1, and simply oxidation reaction condition is different, and first reactor propylene/oxygen/water steam/
The mol ratio for adding nitrogen is 1/1.6/1.0/2.4, and the mol ratio that second reactor adds oxygen/propylene is 0.5, reaction temperature
Respectively 332 DEG C and 266 DEG C, acrylic acid yield is 88.3%.
(2) acrylic acid separation and purification purifies：
As shown in figure 1, it is N that reaction zone exit reactant mixture 300, which is composition,2(68.9wt%), COx (2.4wt%),
O2(3.7wt%), propylene (0.2wt%), acrylic acid (14.0wt%), acetic acid (0.4wt%), water (8.9wt%) and maleic acid
(0.01%) the gaseous mixture containing acrylic acid, the gaseous mixture 300 is sent into from the bottom of tower bottom acrylic acid absorption and separation tower 100 should
Absorption tower 100, gaseous mixture composition are same as above.Enter absorption tower after distillate 201 from the top of acrylic acid purifying column 200 is heated
100 bottom fillings.
Phegma 101 is prepared in condensing unit 102 first, after phegma acrylic acid content is qualified
(＜ 0.5wt%) uses phegma backflow instead, reaches the purpose of partial condensation.Tower top pressure is controlled by tail gas regulating valve.
By adjusting tower reactor heating amount, control bottom temperature 85 ± 0.5 (DEG C), tower top temperature 67.5 ± 0.5 (DEG C), tower reactor
Acrylic acid content ＜ 75wt% in solution, acrylic acid content in overhead condensation liquid<0.5wt%.
The tower reactor solution of acrylic acid absorption and separation tower enters acrylic acid purifying column, specifically comprises acrylic acid
(72.7wt%), acetic acid (6.3wt%), water (11.8wt%) and maleic acid (0.2wt%), acrylic acid purifying column main function are
Acrylic acid liquid phase mixture, side take-off acrylic acid are separated, tower top is shown in Fig. 1 without backflow, flow.Tower reactor discharge rate is controlled in 1.2-
1.3wt%, tower top discharge rate 56.8%, side take-off purity of acrylic acid product is less than 95.0wt%.Separation acrylic acid is not reached
Purpose.
Comparative example 4
Catalyst preparation and oxidation reaction：
(1) prepared by O composite metallic oxide catalyst：
Catalyst preparation process is with embodiment 1, simply from the Si powder less than 40 μm.
(2) propylene oxidation reaction：
As a result oxidation reaction condition is shown, first reactor and second reactor temperature are respectively 346 DEG C with embodiment 1
With 280 DEG C, acrylic acid yield be 78.8%.
Claims (19)
1. a kind of carbon monoxide-olefin polymeric for propylene oxidation production acrylic acid, it includes the first catalyst and the second catalyst；
First catalyst is the Mo-Bi composite oxide catalysts for having general formula：
Mo12BibFecCodNieXfYgOh
Wherein, X is selected from least one of W, Sb, Ce, Cr, Mn, La element；
Y is selected from least one of Na, K, Li, Rb, Cs, Ca, Mg, Sr and Ba element；
B is 0.5~3；
C is 0.5~3；
D is 3~8；
E is 1~5,
F is 0.05~2,
G is 0.05~1；
H is the numeral that is determined by the oxidation state of above-mentioned each element；
The Mo-Bi composite oxide catalysts are using made from following method：
A) mixture of each element precursor, co-precipitation are provided, and are dried to obtain powder；
B) gross weight meter of final mixture is pressed, the particle diameter for adding 5%~40wt% is 70~220 μm of Si powder, and is molded；
C) it is 400h in air speed by obtained article shaped-1To 1200h-1Air in 160~250 DEG C be calcined 15~30 hours；
Then it is calcined 4~20 hours at 450~530 DEG C；
Second catalyst is the Mo-V composite oxide catalysts for having general formula：
Mo12VbCucWdXeYfOg
Wherein X is selected from least one of Nb, Sb, Sr, Ba, Ni element；
Y is selected from least one of La, Ce, Nd, Sm element；
B is 2~6；
C is 0.5~3；
D is 0.5~3；
E is 0.1~4；
F is 0.01~2；
H is the numeral that is determined by the oxidation state of above-mentioned each element；
The Mo-V composite oxide catalysts are as made from following method：
A) mixture of each element precursor is provided, be co-precipitated and dry, obtain powder；
B) gross weight meter of final mixture is pressed, the Si powder that 40%~65wt% particle diameters are 70~220 μm is added, shaping, obtains
To article shaped；
C) by the article shaped the ammonia containing 3%~30vol%, 3%~10vol% oxygen and surplus nitrogen gaseous mixture
It is calcined 4~18 hours in 240~300 DEG C in body, in 350~400 in the atmosphere that oxygen content is more than 3vol% and surplus nitrogen
DEG C roasting 3~18 hours.
2. carbon monoxide-olefin polymeric as claimed in claim 1, it is characterised in that first catalyst has general formula
Mo-Bi composite oxide catalysts：
Mo12BibFecCodNieXfYgOh
Wherein, X is at least one element selected from W, Sb, La；
Y is at least one element selected from Na, K, Ca；
B is 0.7-2.8；
C is 0.8-2.8；
D is 3-8；
E is 1.4-4.5；
F is 0.05~2；
G is 0.05~1.
3. carbon monoxide-olefin polymeric as claimed in claim 2, it is characterised in that
B is 0.9-2.5；
C is 1.0-2.6；
D is 4.0-7.5；
E is 1.6-4.0；
F is 0.08-1.9；
G is 0.08-0.9.
4. carbon monoxide-olefin polymeric as claimed in claim 3, it is characterised in that
B is 1.2-1.8；
C is 1.8-2.2；
D is 5.19-5.62；
E is 2.3-2.8；
F is 0.3-1.4；
G is 0.13-0.5.
5. such as the carbon monoxide-olefin polymeric any one of claim 1-4, it is characterised in that first catalyst is selected from
Mo12Fe1.84Co5.19Ni2.40Bi1.69K0.11Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.48Fe2.03Co5.62Ni2.40Bi1.28K0.12Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12Fe1.88Co5.25Ni2.48Bi1.89K0.18Na0.07Ca0.10Sb0.12La0.86Oh；
Mo12W0.58Fe2.13Co5.42Ni2.30Bi1.30K0.15Na0.05Ca0.09Sb0.10La0.76Oh；
Mo12W0.50Fe1.93Co5.01Ni2.42Bi1.50K0.18Na0.15Ca0.09Sb0.18La0.92Oh；
Mo12Fe1.98Co4.95Ni2.32Bi1.85K0.08Na0.17Ca0.21Sb0.18La0.96Oh；Or the mixture of its two or more formation.
6. such as the carbon monoxide-olefin polymeric any one of claim 1-4, it is characterised in that under first catalyst uses
Made from row method：
A) mixture of each element precursor, co-precipitation are provided, and are dried to obtain powder；
B) gross weight meter of final mixture is pressed, adds the Si powder of 8-38 weight % 70~220 μm of particle diameter, and is molded；
C) it is 400h in air speed by obtained article shaped-1To 1200h-1Air at a temperature of 160~250 DEG C roasting 15~
30 hours；Then it is calcined 4~20 hours at 450~530 DEG C.
7. carbon monoxide-olefin polymeric as claimed in claim 6, it is characterised in that first catalyst is made using following method
's：
A) mixture of each element precursor, co-precipitation are provided, and are dried to obtain powder；
B) gross weight meter of final mixture is pressed, adds the Si powder of 10-35 weight % particle diameter 70-210 microns, and is molded；
C) it is 450h in air speed by obtained article shaped-1To 1000h-1Air in, be calcined 18- at a temperature of 160~240 DEG C
28 hours；Then 6-18 hours are calcined at 460~520 DEG C.
8. such as the carbon monoxide-olefin polymeric any one of claim 1-4, it is characterised in that under first catalyst uses
Made from row method：
A) mixture of each element precursor, co-precipitation are provided, and are dried to obtain powder；
B) gross weight meter of final mixture is pressed, adds the Si powder of 15-30 weight % particle diameter 70-160 microns, and is molded；
C) it is 600h in air speed by obtained article shaped-1To 850h-1Air in 22-24 is calcined at a temperature of 170-210 DEG C
Hour；Then 11-13 hours are calcined at 480-500 DEG C.
9. carbon monoxide-olefin polymeric as claimed in claim 1, it is characterised in that second catalyst has general formula
Mo-V composite oxide catalysts：
Mo12VbCucWdXeYfOg
Wherein X is at least one element selected from Sb, Sr, Ba, Ni；
Y is La and/or Ce；
B is 2.2-5.6；
C is 0.6-2.8；
D is 0.7-2.8；
E is 0.1-3.7；
F is 0.02-1.8；
H is the numeral that is determined by the oxidation state of above-mentioned each element.
10. carbon monoxide-olefin polymeric as claimed in claim 9, it is characterised in that
B is 2.4-5.0；
C is 0.7-2.6；
D is 0.8-2.6；
E is 0.1-3.2；
F is 0.03-1.6；
H is the numeral that is determined by the oxidation state of above-mentioned each element.
11. carbon monoxide-olefin polymeric as claimed in claim 9, it is characterised in that
B is 3-4.5；
C is 0.9-2.0；
D is 1.0-2.2；
E is 0.1-2.8；
F is 0.05-1.2；
H is the numeral that is determined by the oxidation state of above-mentioned each element.
12. such as the carbon monoxide-olefin polymeric any one of claim 9-11, it is characterised in that second catalyst is selected from
Mo12V3.05W1.12Cu0.98Sb1.71Sr0.25Ni0.13Ba0.09La0.05Oh；Mo12V3.75W1.12Cu1.22Sb1.86Sr0.30La0.05Oh；
Mo12V3.25W1.02Cu0.88Sb1.21Sr0.15Ni0.23Ba0.07La0.06Oh；
Mo12V2.95W1.18Cu1.08Sb1.75Sr0.20Ni0.20Ba0.08La0.06Oh；Mo12V3.85W1.02Cu1.25Sb0.89Sr0.35La0.06Oh；
Mo12V3.25W1.22Cu1.02Sb1.76Sr0.28La0.07Oh；Or the mixture of its two or more formation.
13. such as the carbon monoxide-olefin polymeric any one of claim 1 or 9-11, it is characterised in that second catalyst is
As made from following method：
A) mixture of elemental precursors is provided, be co-precipitated and dry, obtain powder；
B) gross weight meter of final mixture is pressed, the Si powder that 42-62 weight % particle diameters are 70~220 μm is added, shaping, obtains
Article shaped；
C) by the article shaped the ammonia containing 3%~30vol%, 3%~10vol% oxygen and surplus nitrogen gaseous mixture
In body, it is calcined 4~18 hours for the first time in 240~300 DEG C；
It is calcined 3~18 hours for second in 350~400 DEG C in the atmosphere that oxygen content is more than 3vol% and surplus nitrogen.
14. such as the carbon monoxide-olefin polymeric any one of claim 1 or 9-11, it is characterised in that second catalyst is
As made from following method：
A) mixture of elemental precursors is provided, be co-precipitated and dry, obtain powder；
B) gross weight meter of final mixture is pressed, the Si powder that 48-58 weight % particle diameters are 70-180 microns is added, shaping, obtains
To article shaped；
C) by the article shaped the ammonia containing 10%~20vol%, 6%~7vol% oxygen and surplus nitrogen mixing
In gas, 6-12 hours are calcined for the first time in 250-290 DEG C；
In 360-390 DEG C of second of roasting 6-12 hour in oxygen content is more than 7vol% and surplus for the atmosphere of nitrogen.
15. a kind of aoxidize manufacture acrylic acid by propylene, it includes：
(a) the first and second catalyst in the carbon monoxide-olefin polymeric as any one of claim 1-14 are put respectively
In two conversion zones；
(b) raw mixture containing propylene, oxygen and optional vapor is passed sequentially through the conversion zone, obtain reaction mixing
Thing, the volume ratio of vapor and propylene is 0-0.8 in the raw mixture：1；
(c) reactant mixture is passed through and isolates and purifies area, separation by what acrylic acid absorption and separation section and acrylic acid rectifying section formed
Obtained acrylic acid.
16. method as claimed in claim 15, it is characterised in that the volume ratio of vapor and propylene in the raw mixture
For 0.05-0.7：1.
17. it is a kind of for propylene oxidation manufacture acrylonitrile-acrylic acid reaction system, it by reaction zone with isolate and purify district's groups into；
The reaction zone is made up of concatenation first reactor and second reactor, and first and second reactor is equipped with such as right
It is required that the carbon monoxide-olefin polymeric any one of 1-7；
The area that isolates and purifies is made up of acrylic acid absorption and separation section (100) and acrylic acid rectifying section (200)；
The second reactor outlet is connected with the bottom gas inlet (203) of the acrylic acid absorption and separation section (100), described
The outlet at bottom (105) of acrylic acid absorption and separation section (100) is connected with the upper entrance (106) of acrylic acid rectifying section (200).
18. reaction system as claimed in claim 17, it is characterised in that the top of the acrylic acid absorption and separation section (100) is also
Including a liquid outlet (101) being connected with condenser (102) and the liquid inlet being connected with the condenser (102) (103,
104), for using after a part of gas condensation in segregation section as absorbing liquid.
19. the reaction system as described in claim 18 or 17, it is characterised in that go out at the top of the acrylic acid rectifying section (200)
Mouth (205) is connected with the bottom liquid inlet (202) of the segregation section (100), and the bottom liquid inlet (204) is positioned at described
The top of bottom gas inlet (203).
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|---|---|---|---|---|
| US4250054A (en) * | 1976-06-01 | 1981-02-10 | The Standard Oil Company (Ohio) | Catalysts for producing unsaturated aliphatic acids |
| CN1343193A (en) * | 1999-03-10 | 2002-04-03 | 巴斯福股份公司 | Method for catalytic gas phase oxidation of propene into acrylic acid |
| CN101579630A (en) * | 2008-05-16 | 2009-11-18 | 住友化学株式会社 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN102775295A (en) * | 2012-08-10 | 2012-11-14 | 上海华谊丙烯酸有限公司 | Method for purifying acrylic acid |
| CN103721722A (en) * | 2012-10-10 | 2014-04-16 | 上海华谊丙烯酸有限公司 | Composite oxide catalyst and preparation method thereof |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4250054A (en) * | 1976-06-01 | 1981-02-10 | The Standard Oil Company (Ohio) | Catalysts for producing unsaturated aliphatic acids |
| CN1343193A (en) * | 1999-03-10 | 2002-04-03 | 巴斯福股份公司 | Method for catalytic gas phase oxidation of propene into acrylic acid |
| CN101579630A (en) * | 2008-05-16 | 2009-11-18 | 住友化学株式会社 | Method for producing catalyst for use in production of unsaturated aldehyde and/or unsaturated carboxylic acid, and method for producing unsaturated aldehyde and/or unsaturated carboxylic acid |
| CN102775295A (en) * | 2012-08-10 | 2012-11-14 | 上海华谊丙烯酸有限公司 | Method for purifying acrylic acid |
| CN103721722A (en) * | 2012-10-10 | 2014-04-16 | 上海华谊丙烯酸有限公司 | Composite oxide catalyst and preparation method thereof |
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