CN101279904A - Improved method for preparing aromatic carboxyl acid - Google Patents
Improved method for preparing aromatic carboxyl acid Download PDFInfo
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Abstract
Disclosed is a method to prepare aromatic carboxylic acid from aromatic compounds with alkyl groups through oxygenation. The aromatic compounds with alkyl groups are oxidized by the mixture of oxygen-containing gas and recycling exhaust gas under the existence of activator and liquid solvent in an oxidation reactor. Since a small amount of exhaust gas is discharged into the atmospheric air, exhaust gas disposal process is evidently simplified. The method is of great significance in economic aspect and the aspect of environment protection.
Description
Technical field
The invention provides the manufacture method of a kind of aromatic carboxylic acid (for example pure terephthalic acid (PTA) (PTA)), wherein Alkylaromatics in liquid solvent and in the presence of the catalyst system that comprises cobalt, manganese and bromine by the oxidative gas mixture oxidation of oxygen-containing gas raw material and cycle gas (offgas).Described gas raw material is to have high oxygen concentration, is more preferably the oxygen-containing gas mixture of pure oxygen.Therefore, can significantly reduce the watt consumption of compressing in the described gas raw material process.From the waste gas of described oxidation reactor by condensation and/or optional absorption, absorption or chemical reaction with the solvent that reclaims evaporation with from waste gas, remove organism and/or form CO
x(CO
2And CO) is the part round-robin afterwards at least.
Background technology
According to the technology of going into operation, most of waste gas is the rare gas element of any kind, for example nitrogen, carbonic acid gas, argon gas, helium and their mixture.Because the pressure of cycle gas is near reaction pressure, therefore, only need less power with described waste gas circulation in described oxidation reactor.Compare routine techniques, the advantage of technology of the present invention comprises: the capital investment in (1) capital investment still less, particularly off gas treatment, and this is because the waste gas much less of need handling, and off gas treatment is obviously simplified even saved; (2) running cost aspect electric power, water coolant and fuel is much lower, although owing to use oxygen rich gas to cause raw materials cost to rise in gas raw material; (3) the bigger oxygen concn scope in oxidation reactor ingress, it can be adjusted in the scope of 0-100% basically easily, although be more preferably high-concentration oxygen (＞21%), to enlarge the ability of described oxygen reaction device.Use the existing technology of conventional air or oxygen-rich air to improve based on technology of the present invention.
The method of making the aromatic carboxylic acid is well-known, and industrial widely-used.For example, in the presence of cobalt-manganese-bromine, under the high temperature and high pressure condition, can generate aromatic carboxylic acid, for example terephthalic acid (terephthalic acid), phthalic acid (orthophthalic acid) or m-phthalic acid (isophthalic acid) by the corresponding Alkylaromatics of oxidation (being p-Xylol, o-Xylol and m-xylene) or its intermediate of oxidation.Preparation aromatic carboxylic acid's conventional process can be referring to United States Patent (USP) 2833816,4329493,4593122,4827025 and 5183933.Behind the purifying of necessity, these polycarboxylic acids are as the raw material of preparation polyester, and described polyester is widely used in synthon, film or the like.The industrially preparing process of PTA mainly is Amoco method and changing method thereof, for example MPC and Eastman method.The main difference of these technology is PX oxidation types with reactor.
The synoptic diagram of common process as shown in Figure 1.Air is usually as oxygenant.Randomly, add pure oxygen, improve the ability of equipment to form oxygen rich gas as oxygenant.Described oxygen pipeline 20 leads to oxygen compressor 20A, and leaves through pipeline 21.Air arrives air compressor 11A through pipeline 11, and leaves through pipeline 12.After the compression, air or oxygen-rich air are delivered to the bottom of reactor 24 through pipeline 13.Alkylaromatics is sent into through pipeline 22, and flow through pipeline 23 of product reclaims.The oxidation of the Alkylaromatics temperature between 175-225 ℃ is usually carried out.Selective reaction pressure makes the sour solvent of 70-80% remain on liquid phase.The reaction liberated heat makes some acetic acid solvent evaporations.
Gained gas comprises a large amount of acetate, water, nitrogen and a spot of oxygen, carbonic acid gas and other organic compound usually in the pipeline 14.Described waste gas is condensation in the condenser system 14A that water coolant charging 14B and vent line 14C are housed at first, and most of in all condensation products or all turn back in the reactor through pipeline 19.Described gas leaves described condenser 14A through pipeline 15 and enters gas-liquid separator 15A.Then, uncooled waste gas is delivered in the high pressure scrubber (scrubber) through pipeline 16, wherein by removing extra acetate with water or acetic acid aqueous solution counter current contact from described gas.Washer 16A has water/acetic acid aqueous solution feeding line 16C and washer bottom line 16B.Before entering atmosphere, the oxidation gaseous effluent in the pipeline 17 is handled through following steps usually: the catalyticcombustion 19 of organic compound, carry out energy recovery and remove bromine by washing with caustic solution by the expansion in the internal combustion turbine.Catalytic combustion reactor 19 has fuel and air feed pipeline 19A and head outfall pipeline 18.According to ICI patent (WO9639595), described catalyticcombustion working load carries out in 350-700 ℃ temperature range at platinum on the inert support and/or palladium catalyst.For perfect combustion, need to use for example Sweet natural gas of extra fuel.
Done very big effort by improving catalyst system (United States Patent (USP) 5112992), optimized reaction conditions, promptly temperature of reaction, pressure and time constantly improve capacity of equipment and improve quality product and cost competitiveness.By using the oxygen coalescence technology can obviously improve the quality of throughput and described product, in the described oxygen coalescence technology, oxygen-rich air replaces conventional air as oxygenant especially.Oxygen concentration in the oxygen-rich air is by regulating recently changing of oxygen and air.United States Patent (USP) 5371283 discloses a kind of technology, and wherein owing to use pure oxygen as oxygenant, described oxidation is efficiently.But,, can find out easily that disclosed reactor design is quite complicated in this patent, and a large amount of nitrogen must be sent in the gas-phase space of described reactor in order to reduce flammable danger in the technology.For security consideration, oxygen concentration in fact still is controlled in the scope of 21-28%.
In principle, the oxygen-containing gas mixture of any oxygen and rare gas element (for example oxygen and nitrogen, oxygen and helium and oxygen and carbonic acid gas) can be used as oxygenant in making aromatic carboxylic acid's process.Air and oxygen-rich air worldwide have been used to make the aromatic carboxylic acid.Although CO
2Itself be not oxygenant, but reported CO
2Change into aromatic carboxylic acid for the Alkylaromatics partial oxygen and have promoter action (S.EPark etc., Catal.Lett.Vol.81.No.3-4, in August, 2002,169-173 page or leaf).According to this paper, United States Patent (USP) 6180822 and 6194607 proposes mixture with oxygen and carbonic acid gas as the oxygenant in the Alkylaromatics partial oxidation.
United States Patent (USP) 5371283 and 5523474 discloses a kind of PTA preparation technology, wherein purity oxygen or approach pure oxygen be used as oxygenant in specially designed liquid-phase oxidation reactor (LOR).Although, can easily find out in the top gas phase that a large amount of nitrogen must be sent in the reactor, to reduce flammable danger by using very pure oxygen can obviously improve the throughput of described equipment.And specially designed LOR is quite complicated.United States Patent (USP) 5693856 discloses a kind of improvement technology, wherein from oxidation reactor and mainly comprise CO
2Burn in the oxidizing fire reactor with organic waste gas, cooling (chill) is partly recirculated in the reactor at last at least then, uses pure oxygen or the problematic explosion potential during as oxygenant near pure oxygen to alleviate.In United States Patent (USP) 5693856 disclosed technologies, described waste gas is partly recirculated in the described reactor at the different sites of reactor.And at least a portion cycle gas injects the top gas phase of described reactor, and reducing flammable or risk of explosion, and remaining cycle gas directly adds in the liquid phase.United States Patent (USP) 5693856 disclosed technologies are compared United States Patent (USP) 5371283 disclosed technologies more can reduce flammable danger, and this is because use CO
2Rather than N
2As the thinner in the reactor head space.
Preparation aromatic carboxylic acid's (particularly PTA) oxidation technology is developed in a large number.This Technology is now near the point on income (returns) pinnacle, and the not other key breakthrough of expectability, i.e. new catalyst system and better operation.The PTA manufacturer is just wishing further to improve equipment capacity and quality product, by the operation conditions optimization (O in temperature, pressure, the gas raw material for example
2Concentration and energy synthesis) the reduction running cost.The invention provides a kind of new technology, wherein pure oxygen or oxygen rich gas mixture are as oxygenant; The high pressure exhaust gas that mainly comprises rare gas element after optionally treating to small part even all be circulated back in the described reactor.And, round-robin waste gas more preferably with gas raw material pre-mixing before sending into described reactor, so just can obtain equally distributed oxygen.
Summary of the invention
In an embodiment of the invention, disclose a kind of aromatic carboxylic acid's of preparation method, described method comprises: the mixture oxidizing alkylaromatic compounds of using oxygen rich gas and cycle gas in the presence of catalyzer and liquid solvent.
The invention provides improving one's methods of preparation pure aromatic carboxylic acid, particularly pure terephthalic acid (PTA).Discuss for convenience, will describe the present invention in detail, prepare PTA, although the present invention is equally applicable to other aromatic polycarboxylic acid of preparation because the present invention is applicable to by oxidation of p-xylene (PX).
The invention discloses a kind of novel method, wherein at least a portion even almost all be circulated back to oxidation reactor afterwards through optionally treating (for example condensation or absorption) from the waste gas of oxidation reactor.Only a small amount of waste gas that in oxidising process, forms or the CO that only in oxidising process, forms
x(CO
2And CO) and some by products (being the trace bromide) need from described system, remove.The objective of the invention is to improve the PTA throughput of existing installation, with undesirable by product (4-carboxyl benzaldehyde (4-carboxybenzadldhyde for example, formation 4-CBA)) is reduced to minimum or is made it and eliminates, reduction equipment, material and running cost, and the quality that improves the PTA product.
PTA is in industrial following manufacturing: PX and oxygen-containing gas (for example air) are reacted in the presence of catalyzer, bromide-based initiator and solvent (being acetate).The improvement of producing for PTA at present comprises raising increment productivity and reduces manufacturing cost.Oxygen concentration is a kind of improving one's methods of existing installation throughput of improving.In order further to improve described throughput, particularly reduce running cost, the invention discloses a kind of novel method, wherein pure oxygen or oxygen rich gas mixture replace air as oxygenant, and described waste gas is to small part even all be recycled to described oxidation reactor.The rare gas element that is present in the described cycle gas mainly is CO
xAnd N
2, perhaps the both is a main component, this depends on rare gas element and operational condition used when described method is gone into operation.
Because be used as the oxygenant of the inventive method with cycle gas blended pure oxygen or oxygen rich gas mixture, thus oxygen concentration can easily be regulated, and remain in the safety range.Usually, in order to improve throughput, be more preferably high-concentration oxygen (＞21%).Therefore, the inventive method has all advantages that method provided of using the oxygen concentration technology, for example owing to the higher throughput that improves existing installation of oxygen concentration in the incoming flow.
By diluting with cycle gas, the oxygen concentration in the reactor can easily be controlled in the safety range.Inflammableness potentially dangerous described in the United States Patent (USP) 5371283 (wherein pure oxygen is as oxygenant) has in fact been eliminated in the method for the invention.Because the present invention needn't change the O in the described reaction conditions, particularly oxidation reactor
2Concentration (it can keep identical with ordinary method) does not therefore need to change described oxidation reactor.
And owing to can use pure oxygen, and described waste gas circulates with the working pressure near the inventive method, so the required power of pressurized gas raw material is compared ordinary method (the inertia N that wherein is used for pressurized air
2Wasted a large amount of power) lower.
When in cycle gas, there being certain density carbonic acid gas (CO
2) time, speed of reaction and all can obviously improve for the selectivity of terephthalic acid (TA), this is because CO
2For PX oxidation have promoter action (Sang-Eon Park etc., Catal.Lett., 81 (2002), 169-173).Therefore, compare conventional PTA manufacture method, the inventive method needs the shorter reaction time to reach identical PX transformation efficiency.In the identical reaction times, need be for given PX transformation efficiency the present invention than low reaction temperatures.For given oxidation reactor, this means higher throughput or less capital investment.And, because at CO
2Exist the impurity that in oxidising process, forms down less, therefore also can improve the quality of PTA.
The most important thing is that no matter use which kind of rare gas element in described method, the technology of the application of the invention can obviously reduce capital investment and the running cost in the off gas treatment.The waste gas of described oxidized portion comprises rare gas element, excessive oxygen and trace organic substance (for example non-switched PX, the hydrocarbon derivative by product such as methyl acetate and evaporable acetate).Before discharging into the atmosphere, described waste gas must be handled by absorbing with catalyticcombustion subsequently.In the catalytic fuel reactor, need to use extra fuel (for example Sweet natural gas) that the temperature of described waste gas is brought up to temperature of reaction (about 600-700 ℃).In method disclosed herein, this off gas treatment can obviously be simplified or eliminate, and this is because only need to discharge small amount of exhaust gas.Randomly, using separating unit tentatively to remove is the CO that a small amount of deep oxidation PX and burning acetic acid solvent form
xAnd/or the organism of trace (for example methyl bromide), wherein use some improved sorbent material/absorption agents, for example ionic liquid or absorbent charcoal material.Also can be chosen in and handle a small amount of waste gas of discharging in the conventional catalytic combustion reactor.
The accompanying drawing summary
Fig. 1 is the synoptic diagram that is used to prepare the method for pure terephthalic acid (PTA).
Fig. 2 is the synoptic diagram that utilizes the pure terephthalic acid (PTA) preparation method of the inventive method.
Embodiment
The present invention includes PX as follows in liquid phase partial oxidation prepare TA: pure oxygen or oxygen rich gas mixture replace air as oxygenant, except the CO that forms in the reactor
xOutside waste gas to small part even all circulations.The objective of the invention is to improve PTA throughput, minimum reduced in the formation of undesirable by product (for example 4-CBA) or make it and eliminate, reduce capital and running cost, and the quality that improves the PTA product.
The present invention includes: the waste gas circulation that will comprise rare gas element is mixed described cycle gas and pure oxygen or oxygen rich gas mixture as oxidant feed in described oxidation reactor.The concentration of oxygen in oxidant feed changes by the recycle ratio of regulating waste gas.Before being circulated back to described reactor, in separating unit, from described cycle gas, remove a small amount of CO
x, corrodibility organism (for example methyl bromide) is optional simultaneously removes by advanced person's adsorption/absorption technology.More go through the method that relates to waste gas circulation below.
The aromatic carboxylic acid of available the inventive method preparation is selected from terephthalic acid, m-phthalic acid, phthalic acid (phthalic acid), Tetra hydro Phthalic anhydride (phthalic anhydride), naphthalene dicarboxylic acids, trimellitic acid, trimellitic acid 1,2-anhydride (trimellite anhydride), trimesic acid, pyromellitic acid dianhydride, benzene pentacarbonic acid (benzene petracarboxylic acid), benzene hexacarboxylic acid (benzenehexacarboxylic acid), 4,4 '-diphenyl dicarboxylic acid and phenylformic acid.Preferably, described aromatic carboxylic acid is a terephthalic acid.
The Alkylaromatics that can be used for preparing aromatic carboxylic acid of the present invention is selected from p-Xylol, m-xylene, o-Xylol, 1,1,3,5-Three methyl Benzene, 1,2,4,5-tetramethyl-benzene, pentamethylbenzene, hexamethyl-benzene, dimethylnaphthalene, 4,4 '-dimethyl diphenyl and toluene.
For the present invention, oxygen rich gas refers to comprise gas or the gaseous mixture greater than about 21 volume % oxygen.Preferably, described oxygen rich gas mixture comprises about 21-100 volume % oxygen.
Fig. 2 illustrates the system for preparing PTA with the inventive method, and it comprises oxidation reactor 46, condenser 48, washer 53 and separator 52.In embodiment shown in Figure 2, be compressed to required pressure (pipeline 32) from the low pressure pure oxygen in the pipeline 31 of the air gas separation unit (for example cryogenic air separation unit (ASU), transformation (pressure swing) absorbed air separating unit (PSA) and film air gas separation unit) of any kind with oxygen compressor 30, and mix with cycle gas (pipeline 39).Randomly, described air compresses by the air compressor 40A with feeding line 40 and export pipeline 41, and forms oxygen-rich air as the oxygen-containing gas raw material with the oxygen mix of compressing.Oxygen, cycle gas and/or AIR MIXTURES are sent in the oxidation reactor 46 by pipeline 33.Described oxidation reactor comprises the catalyzer of the catalyst system that preferably contains cobalt, manganese and bromine.Randomly, other transition metal (for example hafnium, zirconium and molybdenum) can be present in the described catalyst system.The any-mode that described gaseous mixture uses in can prior art is sent in the described reactor 46.Described liquid starting material enters reactor by pipeline 45, and product stream reclaims by pipeline 47.
What be positioned at described reactor head or approaching described reactor head is vapor discharge pipeline 34, and it is connected in the described condenser system.Described vapor discharge pipeline 34 enters condenser 48, and water coolant enters condenser by pipeline 48B, and effluent leaves condenser by pipeline 48A.The refrigerative evaporative emissions leaves condenser 48 by pipeline 35, enters separator 52, and described separator 52 can be a gas-liquid separator.Liquid from separator leaves separator by pipeline 42, and turns back to oxidation reactor 46.Waste line 36 is connected to the gas inlet on absorption tower.After handling in the washer 53 of sending into water and/or acetic acid aqueous solution by pipeline 54, about 1.5 crust of the pressure of waste gas are lower than the pressure in the oxidation reactor, and choose wantonly and deliver to separating unit 49 by pipeline 37, and described separating unit 49 can be tentatively to remove CO
2And/or the separator of organic compound or absorption/adsorption tower, described CO
2And/or organism leaves separator 49 by pipeline 50.Remainder of exhaust gas leaves the inlet of separator 49 to recycle compressor 38A by pipeline 38.Subsequently, described waste gas uses the cycle gas compressor to small part even all circulations, and mixes with the oxygen rich gas mixture of compression.The pressure oxidation Alkylaromatics that the mixture of oxygen rich gas and cycle gas clings in about 155-225 ℃ temperature and about 8.5-26.5 in oxidation reactor.Randomly, remainder of exhaust gas is delivered to off gas treatment unit 41 (for example oxidizing fire reactor) by pipeline 43, and discharges into the atmosphere by pipeline 44, and described off gas treatment unit 41 can be a catalyst oxidation reactor.Provide fuel and air by pipeline 56 for catalyst oxidation reactor.
The present invention also further specifies with following embodiment, and wherein except as otherwise noted, part, percentage ratio and ratio all are benchmark with the volume.But described embodiment only is illustrative, and should not think that these embodiment limit the present invention.
Embodiment
Plant-scale terephthalic acid continuous processing is simulated, and the oxidation system of this technology is similar to oxidation system shown in Figure 2.In the following embodiments, simulate based on hypothesis shown in the table 1, specific as follows:
Table 1 is used for the hypothesis of processing simulation
| Throughput | 250000 tons of/year PTA |
| Operating time | 7560 hours/year |
| Reaction conditions | |
| Temperature of reaction | 180±2℃ |
| Reaction pressure | 12.85 crust |
| Catalyzer | The Co-Mn-Br catalyst system |
| Solvent | Acetate |
| Acetate/PX raw material weight ratio | 3.28∶1 |
| Water concentration in the reaction solvent (weight %) | ～10％ |
| The PX transformation efficiency | 99.0％ |
| The TA selectivity | 98.0％ |
| The acetate burning | 3.0％ |
Embodiment 1
The oxygen-rich air as the oxidizing gas raw material that forms with mixing the compressed oxygen in pipeline 32 and 41 and air respectively begins the process of this technology.Subsequently, described gas raw material mixes with cycle gas in the pipeline 39, and sends into the bottom of described oxidation reactor.The saturated acetate of most of evaporation always condenses in the waste gas of automatic oxidation reaction device in condenser system, and turns back in the oxidation reactor by pipeline 42.Waste gas from condenser system washs in washer.About 93.5% waste gas does not turn back in the reactor by pipeline 39 circulations under having situation about further handling.Oxygen concentration in the logistics 33 is fixed on 25%.Remainder of exhaust gas in the logistics 43 is handled by conventional catalytic combustion reactor, discharges into the atmosphere by pipeline 44 subsequently.
Flow of selected logistics (with kilogram/hour be unit) and the analog result under steady state are listed in the table 2.Digital vial line in the bracket.
Table 2
| Component | Oxygen (32) | Air (41) | Gas raw material (33) | Liquid starting material (liquid starting material) | Product (product stream) | Cycle gas (38) | The waste gas (43) of discharging |
| O 2 | 19040 | 589.3 | 21040 | 2.32 | 1432.5 | 99.6 | |
| N 2 | 2224 | 33306 | 27.56 | 31115 | 2163.1 | ||
| CO 2 | 26092 | 146.78 | 26011 | 1808.3 | |||
| PX | 46.22 | 19958 | 12.95 | 46.21 | 3.21 | ||
| Acetate | 10.95 | 65407 | 59550 | 10.95 | 0.76 | ||
| Water | 16.7 | 3251 | 5039 | 12490 | 3234.4 | 224.9 | |
| 4-CBA | 2047 | 603.08 | |||||
| TA | 33102 |
In the present embodiment, cycle gas is mainly by 2.32% O
2, 57.6% N
2, 30.7% CO
2And 9.32%H
2O forms.The organism for example concentration of PX and acetate is respectively 226ppm and 95ppm.
Embodiment 2
In the present embodiment, the mixture of pure oxygen (logistics 32) and cycle gas (logistics 39) is sent to the oxidation reactor bottom by pipeline 33.By the oxygen concentration in the flow control pipeline 33 of regulating cycle gas is 25%.Saturated (situated) acetate of most of evaporation always condenses in the waste gas of automatic oxidation reaction device in condenser system, and turns back in the oxidation reactor by pipeline 42.Waste gas from condenser system washs in washer.All CO that in oxidising process, form
2In adsorption/absorption tower 49, from described waste gas, remove, and discharge into the atmosphere.Then, described waste gas all circulates by pipeline 39 and turns back in the reactor.Randomly, described cycle gas is through the absorption tower, and in described absorption tower, ionic liquid is as absorption agent, to remove corrodibility organic compound, particularly methyl bromide.
Flow of selected logistics (with kilogram/hour be unit) and the analog result under steady state are listed in the table 3.Digital vial line in the bracket.
Table 3
| Component | Oxygen (12) | Gas raw material (13) | Liquid starting material (liquid starting material) | Product (product stream) | Cycle gas (18) | Waste gas (the CO that discharges 2And organism) |
| O 2 | 19492 | 20727 | 1.85 | 1234.7 | ||
| N 2 | 49135 | 40.74 | 49135 | |||
| CO 2 | 9.96 | 1877.4 | ||||
| PX | 51.38 | 19958 | 12.68 | 51.38 | ||
| Acetate | 11.15 | 65407 | 59805 | 11.15 | ||
| Water | 3364 | 5039 | 12675 | 3364 | ||
| 4-CBA | 2047 | 603.13 | ||||
| TA | 33105 |
Cycle gas is mainly by 1.95% O
2, 88.59% N
2With 9.43% H
2O forms.The organism for example concentration of PX and acetate is respectively 244ppm and 94ppm.
Embodiment 3
In the present embodiment, the mixture of pure oxygen (logistics 32) and cycle gas (logistics 39) is sent into the oxidation reactor bottom by pipeline 33.The oxygen concentration of controlling in the pipeline 33 by the flow of regulating cycle gas is 25%.The saturated acetate of most of evaporation in condenser system always the waste gas of automatic oxidation reaction device condense, and turn back in the oxidation reactor by pipeline 42.Waste gas from condenser system washs in washer.Subsequently, in absorption tower 49 (wherein having used industrial adsorbents), from waste gas, remove a small amount of CO
2, and finally discharge into the atmosphere.After the washing, waste gas all is circulated back to reactor by pipeline 39 after choosing wantonly and remove trace organic substance (particularly methyl bromide) in adsorption tower, and in described adsorption tower, the gac molecular sieve is as sorbent material.Described isolating CO
2Discharge into the atmosphere.
Flow of selected logistics (with kilogram/hour be unit) and the analog result under steady state are listed in the table 4.Digital vial line in the bracket.
Table 4
| Component | Oxygen (12) | Gas raw material (13) | Liquid starting material (liquid starting material) | Product (product stream) | Cycle gas (18) | Waste gas (the CO that discharges 2And organism) |
| O 2 | 19510.2 | 21020 | 2.31 | 1509.8 | ||
| N 2 | ||||||
| CO 2 | 78309 | 425.45 | 78309 | 1399 | ||
| PX | 50.35 | 19958 | 12.88 | 50.35 | ||
| Acetate | 12.17 | 65407 | 59742 | 12.17 | ||
| Water | 3461.5 | 5039 | 12634 | 3461.5 | ||
| 4-CBA | 2047 | 603.17 | ||||
| TA | 33105 |
Cycle gas is mainly by 2.34%O
2, 88.1%CO
2And 9.52%H
2O forms.The organism for example concentration of PX and acetate is respectively 235ppm and 100ppm.
Embodiment 4
In the present embodiment, the mixture of pure oxygen (logistics 32) and cycle gas (logistics 39) is sent to the oxidation reactor bottom by pipeline 33.By regulating the flow of cycle gas, the oxygen concentration in the pipeline 33 is controlled to be 25%.The saturated acetate of most of evaporation always condenses in the waste gas of automatic oxidation reaction device in condenser system, and turns back to oxidation reactor by pipeline 42.Waste gas from condenser system is handled in washer, and about then 98.3% waste gas is not having to turn back to described reactor by 39 circulations under the situation about further handling.Remaining waste gas is handled through catalytic combustion reactor, discharges into the atmosphere by pipeline 44 subsequently.
Flow of selected logistics (with kilogram/hour be unit) and the analog result under steady state are listed in the table 5.Digital vial line in the bracket.
Table 5
| Component | Oxygen (12) | Gas raw material (13) | Liquid starting material (liquid starting material) | Product (product stream) | Cycle gas (18) | The waste gas (43) of discharging |
| O 2 | 19522 | 21192 | 2.56 | 1667.3 | 28.8 | |
| N 2 | ||||||
| CO 2 | 79347 | 425.1 | 79363 | 1372.5 | ||
| PX | 49.17 | 19958 | 12.68 | 49.17 | 0.85 | |
| Acetate | 12.19 | 65407 | 58894 | 12.19 | 0.21 | |
| Water | 3468 | 5039 | 12539 | 3467 | 60.0 | |
| 4-CBA | 2047 | 603.12 | ||||
| TA | 33102 |
Described cycle gas is mainly by 2.54%O
2, 88.0%CO
2And 9.39%H
2O forms.The organism for example concentration of PX and acetate is respectively 229ppm and 99ppm.
Embodiment 5
Technology as described under condition identical as described in embodiment 1, carrying out, the oxygen of different being to use more impure (lesspure).Therefore, in order to keep the oxygen concentration in the logistics 33, only about 44.1% waste gas circulation turns back in the oxidation reactor.
Flow of selected logistics (with kilogram/hour be unit) and the analog result under steady state are listed in the table 6.Digital vial line in the bracket.
Table 6
| Component | Oxygen (12) | Air (21) | Gas raw material (13) | Liquid starting material (liquid starting material) | Product (product stream) | Cycle gas (18) | The waste gas (43) of discharging |
| O 2 | 12800 | 7611 | 21082 | 2.34 | 671 | 850.5 | |
| N 2 | 28726 | 51344 | 42.61 | 22618 | 45761.9 | ||
| CO 2 | 1525.5 | 2.34 | 1525.5 | 1933.7 | |||
| PX | 20.83 | 19958 | 14.69 | 20.83 | 26.40 | ||
| Acetate | 5.31 | 65407 | 59129 | 5.31 | 6.73 | ||
| Water | 216.1 | 1813.2 | 5039 | 10961 | 1597.1 | 32024.4 | |
| 4-CBA | 2047 | 602.43 | |||||
| TA |
In the present embodiment, recycle ratio is 44.1%.Cycle gas is mainly by 2.25%O
2, 84.8%N
2, 3.63%CO
2And 9.31%H
2O forms.The organism for example concentration of PX and acetate is respectively 206ppm and 93ppm.
Comparative example
Plant-scale terephthalic acid continuous processing is simulated, and this technology oxidation system is similar to oxidation system shown in Figure 1.In the following embodiments, carry out process simulation based on the identical hypothesis shown in the table 1.
Comparative example 1
This comparative example explanation ordinary method of air as the oxidant production terephthalic acid.Pressurized air (logistics 12) is sent to the bottom of oxidation reactor by pipeline 13.The saturated acetate of most of evaporation always condenses in the waste gas of automatic oxidation reaction device in condenser system, and turns back in the oxidation reactor by pipeline 19.Waste gas from condenser system in the pipeline 16 is handled in washer.Subsequently, waste gas is sent in the catalytic combustion reactor by pipeline 17, and in described combustion reactor, all organic compound combustion Cheng Shui and carbonic acid gas are discharged into the atmosphere by pipeline 18 then.
Flow of selected logistics (with kilogram/hour be unit) and the analog result under steady state are listed in the table 7.Digital vial line in the bracket.
Table 6
| Component | Air (12) | Liquid starting material (liquid starting material) | Product (product stream) | Waste gas (17) | The waste gas (18) of discharging |
| O 2 | 22377 | 3.52 | 2794.6 | 1596 | |
| N 2 | 84456 | 59.13 | 84405 | 105230 | |
| CO 2 | 8.87 | 2044.2 | 6837.6 | ||
| PX | 19958 | 17.29 | 47.22 | ||
| Acetate | 65407 | 55981 | 165.12 | ||
| Water | 635.4 | 5039 | 7828 | 6039.2 | 9933 |
| 4-CBA | 2047 | 601.78 | |||
| TA | 33032 |
Waste gas (pipeline 17) is mainly by 2.12%O
2, 90.34%N
2, 2.14%CO
2And 5.22%H
2O forms.
The organism for example concentration of PX and acetate is respectively 472ppm and 1355ppm.
Comparative example 2
This comparative example explanation ordinary method of oxygen-rich air as the oxidant production terephthalic acid.The mixture of pressurized air (logistics 12) and compressed oxygen (logistics 21) is sent to the bottom of oxidation reactor by pipeline 13.The oxygen concentration of recently controlling in the pipeline 13 by adjusting pure oxygen and air is 25%.The saturated acetate of most of evaporation always condenses in the waste gas of automatic oxidation reaction device in condenser system, and turns back in the oxidation reactor by pipeline 19.Waste gas (logistics 16) from condenser system washs in washer.Subsequently, waste gas is sent in the catalytic combustion reactor by pipeline 17, and in described combustion reactor, all organic compound combustion Cheng Shui and carbonic acid gas are discharged into the atmosphere by pipeline 18 then.
Flow of selected logistics (with kilogram/hour be unit) and the analog result under steady state are listed in the table 8.Digital vial line in the bracket.
Table 8
| Component | Oxygen (21) | Air (12) | Gas raw material (13) | Liquid starting material (liquid starting material) | Product (product stream) | Waste gas (17) | The waste gas (18) of discharging |
| O 2 | 6656 | 14770 | 21426 | 2.78 | 1869 | 1113.3 | |
| N 2 | 55744 | 55744 | 46.4 | 55697.6 | 69796 | ||
| CO 2 | 10.15 | 2010.1 | 5156.1 | ||||
| PX | 19958 | 16.77 | 46.63 | ||||
| Acetate | 65407 | 58525 | 12.987 | ||||
| Water | 419.4 | 419.2 | 5039 | 9283.7 | 3905.4 | 4688.4 | |
| 4-CBA | 2047 | 601.81 | |||||
| TA | 33035 |
Waste gas is mainly by 2.53%O
2, 86.1%N
2, 1.97%CO
2And 9.37%H
2O forms.
The organism for example concentration of PX and acetate is respectively 190ppm and 93ppm.
The comparison of running cost and exhausted air quantity
For above-mentioned all embodiment and comparative example, mainly comprise the running cost of the consumption of used Sweet natural gas in oxygen, electricity, water coolant and the catalytic combustion reactor and as shown in table 9 the comparing of amount of discharging waste gas.With comparative example 1 described common process benchmark as a comparison.
Table 9
Although present invention is described according to described embodiment, can find out many other forms of the present invention and improve is conspicuous for the person of ordinary skill of the art.Appending claims of the present invention should be considered to cover all these conspicuous form and improvement within spirit and scope of the invention usually.
Claims (15)
1. method for preparing the aromatic carboxylic acid, described method comprise in the reactor in the presence of catalyzer and liquid solvent the mixture oxidizing alkylaromatic compounds with oxygen rich gas and cycle gas.
2. the method for claim 1, it is characterized in that described aromatic carboxylic acid is selected from terephthalic acid, m-phthalic acid, phthalic acid, Tetra hydro Phthalic anhydride, naphthalene dicarboxylic acids, trimellitic acid, trimellitic acid 1,2-anhydride, trimesic acid, pyromellitic acid dianhydride, benzene pentacarbonic acid, benzene hexacarboxylic acid, 4,4 '-diphenyl dicarboxylic acid and phenylformic acid.
3. method as claimed in claim 2 is characterized in that described aromatic carboxylic acid is a terephthalic acid.
4. the method for claim 1, it is characterized in that described Alkylaromatics is selected from p-Xylol, m-xylene, o-Xylol, 1,2,3-Three methyl Benzene, 1,1,2,4,5-tetramethyl-benzene, pentamethylbenzene, hexamethyl-benzene, dimethylnaphthalene, 4,4 '-dimethyl diphenyl and toluene.
5. method as claimed in claim 4 is characterized in that described Alkylaromatics is a p-Xylol.
6. the method for claim 1 is characterized in that described oxygen rich gas comprises the oxygen greater than 21%.
7. the method for claim 1 is characterized in that described cycle gas comprises carbonic acid gas and carbon monoxide.
8. the method for claim 1, it is characterized in that described cycle gas before the described aromatic carboxylic acid of contact by condensation or adsorption treatment.
9. the method for claim 1 is characterized in that described catalyzer is the catalyzer that contains cobalt, manganese and bromine.
10. the method for claim 1 is characterized in that described liquid solvent is selected from the saturated fatty acid with 2-6 carbon atom.
11. the method for claim 1 is characterized in that the ratio of oxygen rich gas and cycle gas is regulated by the charging that changes described cycle gas.
12. method as claimed in claim 8 is characterized in that the part of described waste gas drains in the atmosphere after processing.
13. the method for claim 1, it is characterized in that described cycle gas the contact described Alkylaromatics before with described oxygen rich gas pre-mixing.
14. the method for claim 1 is characterized in that the oxygen concentration in the mixture of described oxygen rich gas and described cycle gas is not less than 21 volume %.
15. the method for claim 1, the mixture that it is characterized in that described oxygen rich gas and cycle gas is the described Alkylaromatics of oxidation under the pressure that about 155-225 ℃ temperature and about 8.5-26.5 cling to.
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| CNA2007100968046A CN101279904A (en) | 2007-04-03 | 2007-04-03 | Improved method for preparing aromatic carboxyl acid |
| PCT/IB2008/000777 WO2008120091A2 (en) | 2007-04-03 | 2008-04-02 | Improved manufacturing process for aromatic carboxylic acids |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629066A (en) * | 2017-10-27 | 2018-01-26 | 济南隆凯能源科技有限公司 | The production system and production method for the pyromellitic acid anhydride that a kind of process tail gas recycles |
| CN107963964A (en) * | 2017-11-02 | 2018-04-27 | 华东理工大学 | The preparation method of M-phthalic acid |
| CN108997284A (en) * | 2018-07-16 | 2018-12-14 | 山东冠森高分子材料科技股份有限公司 | The method of chloro-benzoic anhydride is synthesized in continuous flow micro passage reaction |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110128261A (en) * | 2019-02-26 | 2019-08-16 | 沅江华龙催化科技有限公司 | A kind of method of energy-saving and environment-friendly paraxylene air oxidation synthesis terephthalic acid (TPA) |
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| US4334086A (en) * | 1981-03-16 | 1982-06-08 | Labofina S.A. | Production of terephthalic acid |
| JPS6036439A (en) * | 1983-08-09 | 1985-02-25 | Mitsubishi Chem Ind Ltd | Production of terephthalic acid |
| JPH078821B2 (en) * | 1986-09-26 | 1995-02-01 | 三井石油化学工業株式会社 | Method for producing aromatic carboxylic acid |
| IN182716B (en) * | 1994-03-22 | 1999-07-03 | Mitsui Petrochemical Ind | |
| ID15851A (en) * | 1996-02-13 | 1997-08-14 | Mitsubishi Chem Corp | PROCESS FOR PRODUCING A CARBOXICIC AROMATIC ACID |
| IT1311976B1 (en) * | 1999-03-25 | 2002-03-22 | Franco Codignola | PROCEDURE FOR THE PRODUCTION OF AROMATIC ACIDS. |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107629066A (en) * | 2017-10-27 | 2018-01-26 | 济南隆凯能源科技有限公司 | The production system and production method for the pyromellitic acid anhydride that a kind of process tail gas recycles |
| CN107629066B (en) * | 2017-10-27 | 2020-11-03 | 潍坊弘润新材料有限公司 | Production system and production method of pyromellitic dianhydride by recycling process tail gas |
| CN107963964A (en) * | 2017-11-02 | 2018-04-27 | 华东理工大学 | The preparation method of M-phthalic acid |
| CN108997284A (en) * | 2018-07-16 | 2018-12-14 | 山东冠森高分子材料科技股份有限公司 | The method of chloro-benzoic anhydride is synthesized in continuous flow micro passage reaction |
| CN108997284B (en) * | 2018-07-16 | 2022-05-03 | 山东冠森高分子材料科技股份有限公司 | Method for synthesizing chlorophthalic anhydride in continuous flow micro-channel reactor |
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| WO2008120091A3 (en) | 2008-12-31 |
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