CN1035762C - Process for producing propenoic acid by homogenization, oxydation and dehydrogenation of propane, and propene oxydation, and apparatus thereof - Google Patents
Process for producing propenoic acid by homogenization, oxydation and dehydrogenation of propane, and propene oxydation, and apparatus thereof Download PDFInfo
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- CN1035762C CN1035762C CN 94118345 CN94118345A CN1035762C CN 1035762 C CN1035762 C CN 1035762C CN 94118345 CN94118345 CN 94118345 CN 94118345 A CN94118345 A CN 94118345A CN 1035762 C CN1035762 C CN 1035762C
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- propane
- propylene
- oxidation
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Abstract
The present invention relates to a method and a united device for preparing acrylic acid by propane which directly carries out homogeneous phase oxidative dehydrogenation and propylene oxidation. The method comprises the steps that a dehydrogenation pipe type reaction furnace, a propylene oxidation reactor and an acrolein oxidation device, etc. are used, and a dehydrogenated reaction mixture is not separated and directly enters the propylene reactor. The method has the advantages of technical step reduction, cost reduction and great yield increase of propylene, acrolein and acrylic acid, and has utilization value in industry.
Description
The present invention relates to hydro carbons (carbon 2-4),, produce method and its machinery of compounds such as vinylformic acid especially by saturated alkane such as propane direct oxidation processing.
At present, the industrial production of hydrocarbon oxides such as propenal, vinylformic acid is used oxidation of propylene now more both at home and abroad.Raw material propylene mainly is the joint product of petroleum hydrocarbon steam pyrolysis system ethene, during the propane cracking, and about 15% (the mole propane) of productivity of propylene, and ethene is 25%.The cracking mix products can not directly advance the propylene oxidation reactor, and cracking is an independent device.
Because of the propylene purposes increasingly extensive, supply shortage, propylene is produced in industrial useful propane heterogeneous catalysis dehydrogenation, is reflected under the hydro condition and carries out, but still because of the catalyst carbon deposition inactivation, need periodic regeneration.Because of hydrogen is arranged in the reaction product, can not directly enter the propylene oxidation reactor and produce hydrocarbon oxide, again so also be independent device.
The research of propane heterogeneous catalytic oxidation dehydrogenation is also arranged, as at V-M
gOn-O the catalyzer, conversion of propane 11-17%, productivity of propylene has only 6-9%.
Also have propane at A
g(B
i-V-M
o-O) being direct oxidation into the research of oxidation products propenal on the catalyzer, transformation efficiency has only 13%, and propenal productive rate 8% is up to 12%.Studies have shown that the effect of catalyst system therefor mainly is that the propylene oxidation that propane homogeneous reaction in the freeboard in the reactor produces is become propenal, so remain a kind of catalyzer based on the propylene oxidation reaction.
In a word, oxidation of propane is produced hydrocarbon oxide still be in conceptual phase, some catalyzer of development, performance need improves, and fails industrialization.
The objective of the invention is to the machinery direct production propylene oxide that a propane homogeneous oxidizing dehydrogenation reactor and propylene reactor (1 or 2) are formed be vinylformic acid etc. method with and device.
Below from comparison to various propane working methods, illustrate purpose of the present invention.
1, the comparison of dehydrogenation of propane homogeneous oxidizing and steam pyrolysis
The homogeneous oxidizing dehydrogenation also is a kind of scission reaction in essence, but with the steam pyrolysis ratio, the former is because of the effect of oxygen, its can producing more propylene, the products distribution of the two by order from big to small is:
Propane homogeneous oxidizing dehydrogenation: C
3H
8, C
2H
4, CH
4, H
2And C
2H
6
Propane steam pyrolysis: CH
4, C
2H
6, C
3H
6, H
2And C
2H
6Especially in the reaction starting stage, this order is more outstanding.
Steam pyrolysis needs high temperature more than 800 ℃ in addition, and cracking furnace pipe is wanted coking; The homogeneous oxidizing dehydrogenation exists because of aerobic, and temperature of reaction is reduced to 500-600 ℃, the reaction tubes noncoking.
Producing more propylene is one of main purpose of the present invention.
2, the comparison of dehydrogenation of propane homogeneous oxidizing and heterogeneous catalytic oxidation dehydrogenation
From experiment of the present invention and document Burch R.and CrabbE.M.Appl.Catal; 100,1993:111-130 all points out, now, during with various catalytic oxidative dehydrogenation catalyzer dehydrogenation, generates the highly selective of propylene under certain conversion of propane, not above the result who is obtained by the homogeneous oxidizing dehydrogenation without catalyzer.
Exploitation needn't be one of purpose of the present invention with the propane homogeneous oxidizing dehydrogenating technology of catalyzer naturally.
3, the comparison of dehydrogenation of propane homogeneous oxidizing and heterogeneous catalysis dehydrogenation
Though catalytic dehydrogenation can obtain higher propylene one-pass yield, but as described in 3, contain hydrogen in the reaction system, reaction product is without separation, can not enter the propylene oxidation reactor, this problem does not exist in the dehydrogenation of propane homogeneous oxidizing, therefore can directly link up the composition machinery to homogeneous oxidizing dehydrogenation and this two reaction process of propylene oxidation, and this is an another main purpose of the present invention.
4, the comparison of dehydrogenation of propane homogeneous oxidizing and propylene oxidation machinery and propane heterogeneous catalytic oxidation
With external Young-Chul Kim at al.Appl.Catal; 70, it is example that the propane heterogeneous catalytic oxidation of the up-to-date report of 1991:175-187 becomes the research of propenal, and because of its transformation efficiency is low, the propenal productive rate is up to 8-12%; But as propane homogeneous oxidizing dehydrogenation product directly being entered the reactor of the commercial catalysts of lower, the interior dress propylene oxidation of temperature acrolein, the propenal productive rate reaches more than 13.5%, than the former height.Utilizing sophisticated propylene oxidation commercial catalysts, exempted from but this step of exploitation raw catalyst, can accelerate the industrialization speed of oxidation of propane processing, also is purpose of the present invention.
According to above comparison, propane homogeneous oxidizing of the present invention dehydrogenation and propylene oxidation are produced the method and the machinery of vinylformic acid etc., more characteristics and advantage are being arranged aspect the hydrocarbon oxide making.General purpose of the present invention is: the propylene oxidation commercial catalysts of packing into different in the subsequent reactor of propane homogeneous oxidizing dehydrogenation, or employing is other subsequent reactions process of raw material with the propylene, make propenal, vinylformic acid, and other carbon 3 hydrocarbon oxides such as propylene oxide etc., effectively utilize the propane resource.
Fig. 1 is the tandem arrangement schema of steam pyrolysis tripping device, propylene oxidation device=self-contained system.
Fig. 2 is a homogeneous oxidizing dehydrogenation reactor propylene oxidation reactor machinery schema.
Fig. 3 a is to be the convection type of pipe still synoptic diagram of heat-transfer medium with the flue gas.
Fig. 3 b is to be the shell and tube reactor synoptic diagram of heat-transfer medium with the fused salt.
The preferably heat supply of the heat carrier of equipment, heat absorption and accumulation of heat make reaction temperature equal Even, keep stable.
Oxidative dehydrogenation under the temperature of having relatively high expectations, during such as 600 ℃, (Fig. 3 is a) to select smoke convection formula tubular react furnace
At 500 ℃ up and down under the lower temperature during oxidative dehydrogenation, select take fused salt to heat carrier Shell and tube reactor (3b). 11 is propane among the figure, and 12 is oxygen, and 13 are the oxidative dehydrogenation product Thing, 14 is flue gas, 15 is fused salt.
Fig. 4 is combined unit flow chart of the present invention, among the figure with
1. the oxidative dehydrogenation of propane homogeneous phase becomes propylene;
2. the propylene heterogeneous catalytic oxidation becomes methacrylaldehyde;
3. the methacrylaldehyde catalytic oxidation becomes acrylic acid; Be example, the formation of expression combined unit.
In two reactors corresponding Industrial Catalysis agent is housed respectively shown in the label 2,3, as
C
o-R
s-B
i-M
o-O catalyst: propylene oxidation becomes methacrylaldehyde to use;
Compound MoCatalyst: acrolein oxidation becomes acrylic acid to use. The number in the figure meaning is as follows: 1, propane oxidative dehydrogenation tubular react furnace: 2, propylene oxidation reactor: 3, propylene formoxy-Change reactor: 4, hydrocarbon oxide water suction tower: 5, gas compressor: 6, propane tower: 7, Cooler: 8, return tank a, raw material propane: b, oxygen: c, oxidative dehydrogenation product: d, benefit Oxygenation and water vapour: e, propylene oxidation product (containing methacrylaldehyde): f, acrolein oxidation product (containing acrylic acid): g, water suction liquid (containing acrylic acid): h, tail gas (discharging): i, ethene return Flow liquid: j, propylene (circulation): k, water vapour: l, water: m, catalyst.
Narrate content of the present invention below in conjunction with accompanying drawing:
1, the oxidative dehydrogenation of propane homogeneous phase and equipment
Raw material propane can be with the refinery's carbon 3 gas fractions that contain 10% following propylene, or separate carbon 3 hydrocarbon that obtain from oil field light hydrocarbon, are oxidant with oxygen, O2/C
3Ratio 0.5-1.5, the reaction temperature Spend 500-600 ℃, time of staying 5-15 second, under low pressure operation is because being exothermic reaction, meeting Focus (the highest) temperature occurs, should suitably control, make it more even. Need only during normal operating Supply with a small amount of heat energy, can select tubular react furnace or shell and tube reactor as:
(1) convection type of pipe stove take flue gas as heat transfer medium; Or (2) shell and tube reactor take fused salt as heat transfer medium.
Used equipment is shown in Fig. 3 a, b.
2, the Direct Catalytic Oxidation of dehydrogenation mixing product and equipment
Generate the propylene of 15-20% after the dehydrogenation of propane homogeneous oxidizing, and 10% the ethene of having an appointment, other is mainly unreacted propane, CO, CO
2A spot of CH
4And C
2H
6, after the suitable heat exchange cooling of dehydrogenation mix products, additional a certain amount of oxygenant behind the adding suitable quantity of water steam, is adorned the subsequent reactor of propylene oxidation commercial catalysts in directly entering, propylene oxidation is become the hydrocarbon oxide such as the propenal of requirement; Can add second oxidation reactor in addition when needing, propenal further is oxidized to vinylformic acid.Catalyst oxidation reactor is with the propylene catalytic oxidation use shell and tube reactor of general industrial usefulness, and as Fig. 3 b, temperature of reaction is different and different with oxidation purpose product, about 250-350 ℃; Reaction tubes exterior-applied liquid medicine steam is heat-transfer medium, with the regulation and control temperature of reaction, reclaims reaction and emits heat.
It is characteristics of the present invention and advantage that the dehydrogenation mix products directly enters follow-up propylene oxidation reactor without separation, need not the pre-separation process, shortened flow process, and the high temperature heat of having utilized products of dehydrogenation reactions to carry, make the machinery flow process simple, energy expenditure is low.Other component in the dehydrogenation product except that propylene comprises unreacted propane etc., plays thermal barrier and thinner in the subsequent oxidation reaction, and is harmless to the propylene oxidation reaction.Contained ethene, if use as chlorohydrination after the oxydehydrogenation, from propylene system propylene oxide, then ethene is reacted into oxyethane simultaneously, as joint product.
3, the recovery of hydrocarbon oxidation products separates
With water absorption method Separation and Recovery purpose oxidation products such as propenal, vinylformic acid.Absorb back gas general fractionating method, reclaim unreacted propane, recycle.Contain ethene, methane in the tail gas, CO, CO
2And a small amount of ethane, can be used as fuel gas or emptying.Ethene also can reclaim when separating propane simultaneously, but condition is more severe.
The present invention is with a propane homogeneous oxidizing dehydrogenation reactor and propylene oxidation reactor (1 or 2), be combined into a machinery of producing hydrocarbon oxide by propane, it and same purpose, the representational tandem arrangement that is combined into by two independent full scale plants are compared as follows:
1, tandem arrangement
Steam pyrolysis tripping device, propylene oxidation device two self-contained systems are in series, and compare as an example.Referring to Fig. 1, Fig. 2.
The key distinction of the two is: tandem arrangement is made up of two cover independent device; And latter's machinery is a covering device, and this mainly just needn't separate owing to the homogeneous oxidizing dehydrogenation product can directly enter follow-up propylene oxidation reactor, and plant construction and process cost are low than tandem arrangement.The two main similarity is that follow-up propylene oxidation reaction process can be with identical conversion unit and catalyzer, and oxidation products Separation and Recovery mode is also identical substantially; But machinery must be with unreacted propane Separation and Recovery in the oxidation products, recycle, and this is because the conversion of propane of machinery homogeneous oxidizing dehydrogenation is low former than propane cracked transformation efficiency in the tandem arrangement.In its tangible tandem arrangement, unreacted propane also need reclaim.
General propylene product price is 3 times of propane; This mainly produces by methods such as petroleum hydrocarbon cracking because of propylene; And machinery changes into propylene with simpler and more direct homogeneous oxidizing dehydrogenation with propane, replaced devices such as cracking, and needn't be separated into propylene product and just enter follow-up propylene oxidation reactor, obtained the hydrocarbon oxidation products identical at last with tandem arrangement, productive expense is low, and the better economic effect is arranged.The machinery flow process as shown in Figure 4.
Below enumerate embodiment and specify the present invention.
Embodiment: (following numerical example is the independent experiment result under the different condition, does not have to connect each other)
1, propane homogeneous oxidizing dehydrogenation
Feed composition: O
2/ C
3(0.55-0.70 mole)
Temperature of reaction: 500-600 ℃; 610 ℃ of hot(test)-spot temperatures
Reaction (stop) time: 2.5-3.0 second
Pressure: normal pressure
Conversion of propane: 45%
Propylene selectivity: 40%
Productivity of propylene: 18%
Ethylene yield: enter the propylene oxidation reactor after the cooling of～10% reaction product.
To the factory of propylene oxidation full scale plant there being, increasing the propane homogeneous oxidizing dehydrogenation reaction equipment of building, dehydrogenation product is introduced the propylene oxidation reactor of full scale plant, also can effectively utilize propane, the system hydrocarbon oxide also belongs to content of the present invention.
2, dehydrogenation of propane homogeneous oxidizing and propylene catalyzed oxidation acrolein
Feed composition: O
2/ C
3(0.85-0.95 comprehensively than)
Reaction conditions:
Oxidative dehydrogenation of propane: 565-570 ℃
Propylene catalyzed oxidation: 325-330 ℃
Reaction times; Second 3.5-4.0 (catalyzed oxidation)
Pressure: normal pressure
Conversion of propane: 36-38%
Productive rate: propenal～13.5%
Ethene 10-12%
The propylene trace reclaims propenal with water absorption method.
3, dehydrogenation of propane homogeneous oxidizing and heterogeneous catalytic oxidation system vinylformic acid
With " propane homogeneous oxidizing dehydrogenation-propylene catalyzed oxidation acrolein-propenal catalyzed oxidation system vinylformic acid " three-step reaction technology is example, corresponding with machinery.
Combined feed total feed is formed: O
2/ C
3(comprising delivery of supplemental oxygen) 1.05-1.09
Temperature of reaction:
Propane homogeneous oxidizing dehydrogenation: with (1)
The propylene Catalytic Oxygen changes into propenal: 320-335 ℃
The propenal Catalytic Oxygen changes into vinylformic acid: 280-320 ℃
Reaction times (two catalyst beds): 2.0 seconds
Pressure: normal pressure
Conversion of propane: 40%
Vinylformic acid selectivity: 37%
Productive rate: vinylformic acid :～14%
Ethene :～10%
Propenal: trace
Propylene: trace
4, other
As the oxidative dehydrogenation of propane product directly being entered such as, can making propylene oxide, get the oxyethane joint product simultaneously with the reactor of chlorohydrination from propylene system propylene oxide.
Light saturated hydrogen except that propane such as ethane, butane also can carry out homogeneous oxidizing dehydrogenation system ethene, butylene etc., further the corresponding hydrocarbon oxide of oxidation system.
Claims (5)
- Produce acrylic acid by direct homogeneous oxidizing dehydrogenation of propane and propylene oxidation for 1 one kinds, enter oxidative dehydrogenation of propane tubular react furnace (1) comprising the propane mixed gas, then enter propylene oxidation reactor (2), the Co-Re-Bi-Mo catalyzer is housed in this reactor, the gas that comes out from (2) enters acrolein oxidation device (3), compound Mo catalyzer is housed in this reactor, then enter hydrocarbon oxide absorption tower (6), what obtain at the bottom of this Tata contains acrylic acid aqueous solution, the gas that comes out from tower (4) cat head enters propane tower (6) after through compressor (5), from the recyclable propane of this cat head, and recycle.
- 2 according to claim 1, and wherein feed composition carbon 2/ carbon 3 of dehydrogenating propane Reaktionsofen (1) is that 0.55～0.70 molar reactive temperature is controlled at 500～600 ℃.
- The dehydrogenation reaction mixture that 3 bases the process of claim 1 wherein directly enters follow-up propylene reactor without separating.
- 4 is to reclaim vinylformic acid in the hydrocarbon oxidation products with water absorption method according to the process of claim 1 wherein, and the gas after absorbing reclaims unreacted propane with general fractionating method, and recycles.
- 5 propane homogeneous oxidizing dehydrogenations and propylene oxidation are produced propenal, acrylic acid machinery, it is characterized in that by oxidative dehydrogenation of propane tubular react furnace (1), propylene oxidation reactor (2), acrolein oxidation reactor (3), hydrocarbon oxide water absorption tower (4), gas compressor (5), propane tower (6) etc. and forming, they are connected in series by the material trend.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94118345 CN1035762C (en) | 1994-11-23 | 1994-11-23 | Process for producing propenoic acid by homogenization, oxydation and dehydrogenation of propane, and propene oxydation, and apparatus thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94118345 CN1035762C (en) | 1994-11-23 | 1994-11-23 | Process for producing propenoic acid by homogenization, oxydation and dehydrogenation of propane, and propene oxydation, and apparatus thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1105352A CN1105352A (en) | 1995-07-19 |
| CN1035762C true CN1035762C (en) | 1997-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94118345 Expired - Fee Related CN1035762C (en) | 1994-11-23 | 1994-11-23 | Process for producing propenoic acid by homogenization, oxydation and dehydrogenation of propane, and propene oxydation, and apparatus thereof |
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Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19622331A1 (en) | 1996-06-04 | 1997-12-11 | Basf Ag | Process of heterogeneously catalyzed gas phase oxidation of propane to acrolein |
| US6541664B1 (en) | 1997-10-21 | 2003-04-01 | Basf Aktiengesellschaft | Method of heterogeneous catalyzed vapor-phase oxidation of propane to acrolein and/or acrylic acid |
| DE19810962A1 (en) * | 1998-03-13 | 1999-09-16 | Basf Ag | Reducing deposition in rectification to separate (meth)acrylic acid from higher boiling organic liquid |
| DE19837517A1 (en) | 1998-08-19 | 2000-02-24 | Basf Ag | Production of acrolein and/or acrylic acid involves two stage catalytic oxydehydrogenation of propane, using modified air with less nitrogen and more oxygen than normal air as the oxygen source |
| DE19837519A1 (en) | 1998-08-19 | 2000-02-24 | Basf Ag | Production of acrolein and/or acrylic acid involves two stage catalytic oxydehydrogenation of propane, using air as the oxygen source and removing nitrogen from residual gas before recycling |
| DE19838795A1 (en) | 1998-08-26 | 2000-03-02 | Basf Ag | Process for the continuous production of (meth) acrylic acid |
| DE19926082A1 (en) | 1999-06-08 | 2000-12-14 | Basf Ag | Process for the purification and production of acrylic acid or methacrylic acid |
| DE19952964A1 (en) | 1999-11-03 | 2001-05-10 | Basf Ag | Process for the catalytic gas phase oxidation to (meth) acrolein and / or (meth) acrylic acid |
| US6566551B2 (en) * | 1999-12-02 | 2003-05-20 | Nippon Shokubai Co., Ltd. | Method for preventing effluent gas pipe from blocking |
| AU2001278449A1 (en) | 2000-06-14 | 2001-12-24 | Basf Aktiengesellschaft | Method for producing acrolein and/or acrylic acid |
| DE10101695A1 (en) | 2001-01-15 | 2002-07-18 | Basf Ag | Heterogeneous catalyzed gas phase production of (meth)acrolein and/or meth(acrylic acid) using mixed oxide catalyst formed into geometrically shaped article of specific geometric characteristics |
| DE102004061772A1 (en) * | 2004-12-22 | 2006-07-06 | Basf Ag | Process for the preparation of propene from propane |
| CN101260033B (en) * | 2008-01-27 | 2010-09-22 | 中国石油集团工程设计有限责任公司东北分公司 | Fresh air temperature control system for preparing acrylic acid by propylene two-step oxygenation method |
| DE102008020688B3 (en) | 2008-04-24 | 2009-11-05 | Evonik Stockhausen Gmbh | Process for the preparation and purification of aqueous phases |
| US8530717B2 (en) | 2008-07-21 | 2013-09-10 | Basf Se | Process for the industrial isolation of propene |
| CN102311334B (en) * | 2010-07-02 | 2013-09-18 | 中国科学院大连化学物理研究所 | Reaction method and reactor for preparing acrylic acid through selective oxidation of propane |
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- 1994-11-23 CN CN 94118345 patent/CN1035762C/en not_active Expired - Fee Related
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