CN100453517C - Method for producing aromatic carboxylic acid and method for producing terephthalic acid - Google Patents
Method for producing aromatic carboxylic acid and method for producing terephthalic acid Download PDFInfo
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- CN100453517C CN100453517C CNB2003801085581A CN200380108558A CN100453517C CN 100453517 C CN100453517 C CN 100453517C CN B2003801085581 A CNB2003801085581 A CN B2003801085581A CN 200380108558 A CN200380108558 A CN 200380108558A CN 100453517 C CN100453517 C CN 100453517C
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- slurries
- pressure
- terephthalic acid
- solid
- aromatic carboxylic
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims description 80
- 238000004519 manufacturing process Methods 0.000 title description 3
- 239000002002 slurry Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 38
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000009835 boiling Methods 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000007791 liquid phase Substances 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims description 47
- 239000000463 material Substances 0.000 claims description 32
- 238000002360 preparation method Methods 0.000 claims description 15
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 11
- 230000006837 decompression Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 alkyl aromatic compound Chemical class 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 229930194542 Keto Natural products 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 125000000468 ketone group Chemical group 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
A process in which the solid-liquid separation of a slurry is conducted by a method by which the slurry can be forcibly filtered while avoiding the precipitation of crystals of an aromatic carboxylic acid within the filter medium without the need of an apparatus for pressurizing the slurry. The process, which is for producing an aromatic carboxylic acid, comprises oxidizing an alkylaromatic compound in the presence of a catalyst in a liquid phase comprising acetic acid as a solvent to generate an aromatic carboxylic acid slurry, crystallizing this slurry, and then subjecting the slurry to solid-liquid separation to recover the crystals of the aromatic carboxylic acid, and is characterized in that the final stage in the crystallization is conducted in a boiling state at a reduced pressure and that in the subsequent solid-liquid separation step, the slurry is filtered under such conditions that the operating pressure on the slurry side is higher than that reduced pressure and the operating temperature is lower than the boiling point of the solvent.
Description
Technical field
The present invention relates to a kind of the preparation aromatic carboxylic acid process in to containing the method that the crystalline slurries carry out solid-liquid separation, also relate to a kind of preparation method of terephthalic acid.
Background technology
As industrial preparation aromatic carboxylic acid method of terephthalic acid for example, known method may further comprise the steps: in acetic acid solvent, in the presence of the catalyzer that contains cobalt, manganese and bromine, with molecular oxygen to alkyl aromatics for example p-Xylol carry out liquid phase oxidation reaction, contain for example terephthalic acid crystalline slurries of consequent aromatic carboxylic acid with the solid-liquid separator processing, reclaim described crystallization then.
An example of this solid-liquid separator is a rotary vacuum filter.This equipment aspirates the inside of cylindrical filter material when the rotating filter material, and order is carried out the suction filtration process of slurries and the flushing process of gained filter cake.
Yet there is a problem in this rotary vacuum filter, and promptly filtering material (for example filter cloth) stops up easily, and this is that the filtrate temperature reduces owing to when making the evaporation of part filtrate through decompression, and the fines that dissolved impurity is separated out sticks on the filtering material.
Blocked when filtering material, throughput just descends, and finally can not carry out to cause production process.At this moment, this equipment will stop, and handle with process of washing, comprise make washing fluid for example water-based caustic soda permeate described filtering material.If often need carry out this flushing, will reduce to produce and render a service.
As reducing this method that needs the number of times of flushing, known method comprises the suction strainer process, the mode that this suction strainer process is carried out is, pressurize to slurries, thereby make filtrate maintenance never can cause oversaturated temperature and pressure condition, suppress aromatic carboxylic acid crystalline deposition (referring to for example patent documentation 1) in the filtering material thus.
[patent documentation 1] spy opens flat 1-299618 communique (claims)
Yet the problem that being used to of above-mentioned prior art contains the solid-liquid separating method of aromatic carboxylic acid crystalline slurries is that this method need be given the suitable pressurised equipment of liquid level of rotary vacuum filter outside surface and described slurries.
Summary of the invention
The objective of the invention is to overcome the problems referred to above, a kind of solid-liquid separating method of slurries efficiently is provided, this method can not separated out the crystallization of aromatic carboxylic acid in filtering material, and does not need to described slurries pressurised equipment.
In order to address the above problem, the present invention has adopted the following method of preparation aromatic carboxylic acid, this method comprises: in acetic acid solvent, in the presence of catalyzer, oxidation of alkyl aromatic compound in liquid phase, to generate the slurries of aromatic carboxylic acid, and make these slurries separate out crystallization, then carry out solid-liquid separation, to reclaim the crystallization of aromatic carboxylic acid, wherein, carry out the described crystalline final step of separating out under the decompression boiling state, and filter these slurries in solid-liquid separation step subsequently, described filtering condition is, the working pressure of slurries one side is higher than the pressure of described decompression state, and service temperature is lower than the boiling point of described solvent.
Preferably filter with compulsory filter type, the pressure difference of filtering material surface and medial surface is 0.01MPa～0.1MPa.By this solid-liquid separation step, can be reduced at and add the equipment of slurries pressure that makes of depressing by filtering material, particularly come the outside and the slurries of the filtering material in the rotary vacuum filter are for example carried out entire pressurisation without any need for special equipment, promptly, even under normal pressure, do not have the aromatic carboxylic acid crystallization in the filtering material yet and separate out, thereby can carry out forced filtration efficiently.
And, separate out in the crystalline final step described, when regulating (attenuating) pressure and make that service temperature is 50 ℃～100 ℃, in than the higher solid-liquid separation step of this pressure, can carry out solid-liquid separation being less than or equal under 100 ℃ the not boiling state.
As the particularly preferred mode of preparation method of terephthalic acid, described preparation method of terephthalic acid comprises that order carries out following steps (i)～(iv), and carries out step (iii) and (iv) in identical equipment:
Step (i), in acetic acid solvent, in the presence of the catalyzer that contains cobalt, manganese and bromine, under the pressure of 1MPa～2MPa, oxidation of p-xylene contains the slurries of terephthalic acid with generation in liquid phase;
Step (ii), the slurries that flash cooling is produced by previous step are so that the terephthaldehyde's acid crystal that is dissolved in the mother liquor is separated out;
Step (iii) makes the terephthalic acid slurries solid-liquid separation of previous step gained by filtration; With
Step is (iv) washed the filter cake that previous step is filtered gained with acetate and/or water,
Wherein, step flash cooling (ii) is by adopting emptying device that pressure is brought down below barometric point to carry out the refrigerative flash distillation under 50 ℃～100 ℃; Described filtration slurries carry out under the following conditions: step (iii) and pressure (iv) be higher than step pressure (ii), service temperature is lower than the boiling point of described solvent.
And, in above-mentioned preparation method of terephthalic acid, preferably carry out step filtration (iii) with compulsory filter type, the pressure difference of filtering material surface and medial surface is 0.01MPa～0.1MPa.
If step (ii) in the temperature of cooling usefulness be decided to be (T) ℃, the feeding temperature that then is used to the acetate that washes and/or water is preferably (T-20) ℃ or is higher than (T-20) ℃, more preferably (T) ℃ or be higher than (T) ℃.Under the pressure when operation, the upper limit of rare gas element temperature is lower than the boiling point of acetate and/or water.
In addition, step (iii) in, carry out solid-liquid separation under the condition of rare gas element charging into, wherein, the temperature of rare gas element preferably be not less than step (ii) in the temperature (T) ℃ of cooling usefulness.Under the pressure when operation, the upper limit of rare gas element temperature is lower than the boiling point of contained solvent in the terephthalic acid slurries.
In the described method for preparing the high purity terephthalic acid, preferably adopt the solid-liquid separation of rotary vacuum filter or level band strainer to operate and carry out step filtration (iii).
Description of drawings
Fig. 1 is a system diagram of describing the solid-liquid separation step of slurries in the embodiment.Wherein, the symbol among the figure is as follows: 1, and crystallizer tank; 2, flash valve; 3, the feed chute of separator; 4, rotary vacuum filter; 6, slurries; 7, filtering material; 7a, inside; 8, emptying device; 9, condenser; 10, pump; 11, vacuum pump; 12, well heater; 13, gas-liquid separator; 14, the washing fluid feed-pipe; 15, the inert gas feed pipe.
Embodiment
As the exemplary of embodiment of the present invention, below will describe in detail and adopt p-Xylol to prepare method of terephthalic acid.
The present invention is an alkylbenzene as the alkyl-aromatic compounds of raw material, for example monoalkylated benzenes, dialkyl benzene and trialkyl benzene, and described alkylbenzene can be converted into aromatic carboxylic acid by liquid-phase oxidation, for example aromatic single-carboxy acid, aromatic dicarboxilic acid and fragrant tricarboxylic acid.Described alkyl-aromatic compounds also comprises the alkylbenzene that has the oxidized alkyl of part.The present invention is particularly preferred for preparing terephthalic acid.At this moment, the alkyl-aromatic compounds as raw material is a p-Xylol.
Aliphatic carboxylic acid solvent preferred rudimentary aliphatic carboxylic acid, for example acetate that the present invention is used.The amount of used solvent is 2～6 times of weight of raw material p-Xylol normally.Acetate more or less contains water, and specifically, can adopt water content is that 10 weight % or the acetate that is lower than 10 weight % are as solvent acetic acid.
For oxidation of alkyl aromatic compound such as p-Xylol, can adopt the gas of molecule-containing keto.Usually adopt air, because air only needs simple device cheaply.In addition, can also adopt the air and the rich oxygen containing air of dilution.
The catalyzer that is used for the oxidation of alkyl aromatic compound comprises the catalyzer that contains cobalt (Co), manganese (Mn) and bromine (Br) conduct formation element.As the particular compound of this catalyst component, cobalt compounds comprises for example Cobaltous diacetate, cobalt naphthenate and cobaltous bromide etc.Manganese compound comprises for example manganese acetate, manganese naphthenate and Manganese dibromide etc.Bromine compounds comprises for example hydrogen bromide, Sodium Bromide, cobaltous bromide, Manganese dibromide and monobromethane etc.
The mode of carrying out oxidizing reaction is, in acetic acid solvent, contain under the situation of catalyzer, at 140 ℃～230 ℃, preferred 150 ℃～210 ℃ gases that feed molecule-containing ketos down continuously with alkyl-aromatic compounds such as oxidation of p-xylene.Reaction pressure is that the gained mixture keeps the pressure of liquid phase or higher pressure at least under temperature of reaction.Described pressure is generally 0.2MPa～5MPa, preferred 1MPa～2MPa.Also may continue oxidation.
Subsequently, the reacting slurry that continues oxidation is reduced to proper temperature and suitable pressure,, separates out crystallization in this step to obtain the terephthalic acid slurries.Separate out preferred 1～6 section of crystalline hop count, more preferably 2～3 sections.
In above-mentioned series of crystallization step, final step is carried out under the decompression boiling state.For reaching the decompression boiling state, the preferred flash cooling of concrete grammar.
Shown in the system diagram of the equipment of Fig. 1, the solid-liquid separating method of the slurries of embodiment may further comprise the steps: will contain the slurries that are dissolved in the terephthalic acid in the acetic acid solvent are filled to final crystallizer tank 1 from flash valve 2 under the decompression boiling state step; Be the solid-liquid separation step that adopts rotary vacuum filter 4 by separator feed tank 3 subsequently, in this solid-liquid separation step, be made as non-pressurized atmosphere by the outside and slurries 6 with filtering material 7, and the inboard 7a of the filtering material 7 that will be rotated slurries 6 is pumped to barometric point or is lower than barometric point, carry out forced filtration thus, peel off and reclaim the terephthalic acid cake that is deposited on the filtering material 7 then.In the figure, label 8 is represented emptying device, 9 condensers for the acetic acid solvent that is used to reclaim evaporation, and 10 is pump.In addition, 11 represent vacuum pump, and 12 is well heater, and 13 is that gas-liquid separator and 14 is the washing fluid feed-pipe.
Described filtering material is preferably made by the metal gauze (thin metal gauze) or the textiles of organic materials, and described organic materials is vibrin, acrylic resin, oxygen Vinyl Ether ketone (PEEK) resin, poly(vinylidene fluoride) (PVDF) resin, polyphenylene sulfide (PPS) resin for example.The filtering material of the preferred ring-band shape of this filtering material, this filtering material be rotation continuously or off and on, so as this with on generate and contain the solid substance (filter cake) of terephthalic acid as main ingredient.
When carrying out forced filtration as mentioned above, this filtering material surface keeps normal pressure, and in final crystallisation step, the medial surface of this filtering material keeps decompression state, form pressure difference thus, so that deposit the pressure that the surface pressure of the band of slurries is higher than this band medial surface.If necessary, also can pressurize and make filtering material surface keep normal pressure or be higher than normal pressure.
Preferably, the pressure difference of described filtering material surface and medial surface is 0.01MPa～0.1MPa.
The feeding temperature of slurries is at least 50 ℃, and preferred 60 ℃～100 ℃, more preferably 70 ℃～90 ℃.When finally separating out the crystalline temperature and being low temperature, help increasing the amount of the aromatic carboxylic acid of recovery.But, if this temperature is too low, just needing the big pressure regulating equipment of decompression degree, this is disadvantageous.
In this way, make the aromatic carboxylic acid slurries that obtain via crystallisation step by having the solid-liquid separating equipment of penetrating filtering material (strainer) structure, so that isolate solvent.Subsequently, with acetic acid solvent or water flush cake.This separation and rinse step not only can adopt rotary vacuum filter to carry out, and can also be undertaken by the belt filter that for example has filtering surface in fact in the horizontal direction.
Be used for separating the equipment with rinse step herein, add washing fluids by washing fluid feed-pipe 14 and come flush cake.If step (ii) in the temperature of cooling usefulness, the temperature of promptly delivering to step slurries (iii) is set at (T) ℃, the temperature of washing fluid preferred (T-20) ℃ or be higher than (T-20) ℃ then, more preferably (T) ℃ or be higher than (T) ℃.By this way, suppressed the filter cake decrease of temperature, prevented crystallization attached to the mother liquor on the described filter cake.
And, be used for separating the equipment with rinse step, when suction filtration,, gaseous fraction and parting liquid are discharged together from the downstream of filtering material by vacuum pump 11.So, from gas feed pipe 15 rare gas element is charged to the upstream of this filtering material, to keep constant compression force in this equipment.As rare gas element, for example, the processing gas that can adopt nitrogen or step (i) to discharge.If step (ii) in the temperature of cooling usefulness, the temperature of promptly delivering to step slurries (iii) is decided to be (T) ℃, the temperature of described gas preferred (T) ℃ or be higher than (T) ℃ then, more preferably (T+10) ℃ or be higher than (T+10) ℃.By this way can suppression equipment built-in function decrease of temperature.Described gas temperature needn't be too high, and when having stipulated temperature (T) ℃, the ideal temperature is (T+100) ℃ or be lower than (T+100) ℃.
Embodiment
Embodiment 1
In acetic acid solvent, under the pressure of 1.5MPa, containing in the presence of the catalyzer of Co/Mn/Br liquid-phase oxidation p-Xylol and make the slurries that contain terephthalic acid.Then, with this slurries flash cooling to 90 ℃, simultaneously, with emptying device with pressure relief to barometric point or be lower than barometric point (0.05MPa).When adopting rotary vacuum filter gained terephthalic acid slurries to be carried out solid-liquid separation by filtration, a side that contacts with slurries in the rotary vacuum filter is set to normal atmosphere, filtrate one side is pumped to barometric point or is lower than barometric point (0.05MPa), simultaneously to the slurries that are in boiling point or are lower than boiling point (90 ℃ the time, the terephthalic acid that contains 35 weight %) carries out forced filtration, separate crude terephthalic acid thus.
And, in next step, the crude terephthalic acid of gained is dissolved in aqueous solvent.In the presence of the 8th family's metal catalyst, the 4-carboxyl benzaldehyde in the solute is reduced.Make it to separate out crystallization by this reduzate of flash distillation, contain terephthalic acid crystalline slurries solid-liquid separation what obtain thus.Dry solid substance obtains highly purified terephthalic acid.
Adopt rotary vacuum filter to filter, carry out solid-liquid separation thus continuously.The time that arrives when stopping up is 55 hours.The result shows, is forced into 0.25MPa with slurries side and the normal conditions that the filtrate side is pumped to 0.2MPa compared rotary vacuum filter, but the time that has obtained being equal to or being longer than the continuous filtration of normal conditions.
Adopt the mode oxidation of p-xylene identical, make the slurries that contain terephthalic acid with embodiment 1.Adopt rotary vacuum filter these slurries of forced filtration (in the time of 91 ℃, containing the terephthalic acid of 35 weight %), separate crude terephthalic acid.Then, the temperature that is filled to the gas of strainer upstream is 100 ℃.At 92 ℃, in rotary vacuum filter equipment, wash this crude terephthalic acid (acetate of 30 weight parts is to the crude terephthalic acid of 100 weight parts) with acetate.Then, use the mode identical to make highly purified terephthalic acid with embodiment 1.
Adopt rotary vacuum filter to filter, thereby carry out solid-liquid separation continuously.The time that arrives when stopping up is 55 hours.
Although describe the present invention in detail with reference to embodiment, those of skill in the art should be understood that, under the situation that does not depart from its spirit and scope, can make various changes and modifications.
The Japanese patent application that the application submitted to based on January 10th, 2003 (special hope 2003-004800) is incorporated herein its full content as a reference.
Industrial applicibility
According to the present invention, under the decompression boiling state, carry out last crystallization step, simultaneously with Carry out solid-liquid separation step under the following condition, namely setting pressure is higher than the pressure in the last crystallisation step Power, operating temperature are lower than the boiling point of solvent. Therefore, can for example be about under the atmospheric normal pressure Force to filter the solid-liquid separation step of slurries. Like this, even without any need for giving filter plant The filtering material outside and the equipment of slurries pressurizations, also can cause hardly the aromatic carboxylic acids knot Force to filter under the brilliant condition of in filtering material, separating out, thereby prevented the stifled of filtering material Plug, have can be stable mode carry out expeditiously the advantage of the Separation of Solid and Liquid of slurries.
Claims (10)
1. method for preparing aromatic carboxylic acid, this method comprises: in acetic acid solvent, in the presence of catalyzer, oxidation of alkyl aromatic compound in liquid phase, to generate the slurries of aromatic carboxylic acid, and make these slurries separate out crystallization, then carry out solid-liquid separation, to reclaim the crystallization of aromatic carboxylic acid, wherein, under the decompression boiling state, carry out the described crystalline final step of separating out, and in solid-liquid separation step subsequently, filter these slurries, described filtering condition is, the working pressure of slurries one side is higher than the pressure of described decompression state, and service temperature is lower than the boiling point of described solvent.
2. the method for preparing aromatic carboxylic acid as claimed in claim 1 wherein, in the crystalline final step, is regulated pressure and is made that service temperature is 50 ℃～100 ℃.
3. the method for preparing aromatic carboxylic acid as claimed in claim 1 or 2, wherein, in solid-liquid separation step, the working pressure of slurries one side is a normal pressure.
4. one kind prepares method of terephthalic acid, and this method comprises that order carries out following steps (i)～(iv), and carries out step (iii) and (iv) in identical equipment:
Step (i), in acetic acid solvent, in the presence of the catalyzer that contains cobalt, manganese and bromine, under the pressure of 1MPa～2MPa, oxidation of p-xylene contains the slurries of terephthalic acid with generation in liquid phase;
Step (ii), the slurries that flash cooling is produced by previous step are so that the terephthaldehyde's acid crystal that is dissolved in the mother liquor is separated out;
Step (iii) makes the terephthalic acid slurries solid-liquid separation of previous step gained by filtration; With
Step is (iv) washed the filter cake that previous step is filtered gained with acetate and/or water,
Wherein, step flash cooling (ii) is by adopting emptying device that pressure is brought down below barometric point to carry out refrigerative under 50 ℃～100 ℃; Described filtration slurries carry out under the following conditions: step (iii) and pressure (iv) be higher than step pressure (ii), service temperature is lower than the boiling point of described solvent.
5. preparation method of terephthalic acid as claimed in claim 4 wherein, is carried out step filtration (iii) with compulsory filter type, and the pressure difference of filtering material surface and medial surface is 0.01MPa～0.1MPa.
6. as claim 4 or 5 described preparation method of terephthalic acid, wherein, if step (ii) in the temperature of cooling usefulness be decided to be (T) ℃, the feeding temperature that then is used to the acetate that washes and/or water is for (T-20) ℃ or be higher than (T-20) ℃.
7. as claim 4 or 5 described preparation method of terephthalic acid, wherein, the acetate that is used for washing and/or the feeding temperature of water are that step is (ii) cooled off the temperature (T) ℃ of usefulness or is higher than (T) ℃.
8. as claim 4 or 5 described preparation method of terephthalic acid, wherein, step is (iii) carried out solid-liquid separation charging under the condition of rare gas element, and, the temperature of rare gas element be step (ii) in cooling usefulness temperature (T) ℃ or be higher than (T) ℃.
9. as claim 4 or 5 described preparation method of terephthalic acid, wherein, being used for step equipment (iii) is rotary vacuum filter or level band strainer.
10. as claim 4 or 5 described preparation method of terephthalic acid, wherein, in solid-liquid separation step, the working pressure of slurries one side is a normal pressure.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4800/2003 | 2003-01-10 | ||
| JP2003004800 | 2003-01-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1735581A CN1735581A (en) | 2006-02-15 |
| CN100453517C true CN100453517C (en) | 2009-01-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801085581A Expired - Lifetime CN100453517C (en) | 2003-01-10 | 2003-12-22 | Method for producing aromatic carboxylic acid and method for producing terephthalic acid |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN100453517C (en) |
| AU (1) | AU2003292740A1 (en) |
| WO (1) | WO2004063135A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121948B (en) * | 2011-11-18 | 2015-04-08 | 中国石油化工股份有限公司 | Method for purifying crude terephthalic acid oxidized sizing agent |
| CN103420828B (en) * | 2012-05-23 | 2015-08-12 | 中国石油化工股份有限公司 | The preparation method of hydrofining crude terephthalic acid reaction raw materials |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064675A (en) * | 1991-02-05 | 1992-09-23 | 帝国化学工业公司 | The preparation method of terephthalic acid |
| JPH09295957A (en) * | 1996-05-07 | 1997-11-18 | Tsukishima Kikai Co Ltd | Production of high-purity aromatic dicarboxylic acid and apparatus therefor |
| CN1278239A (en) * | 1997-10-31 | 2000-12-27 | Hfm国际公司 | Method and apparatus for preparing purified terephthalic acid |
| CN1335296A (en) * | 2000-07-05 | 2002-02-13 | 三菱瓦斯化学株式会社 | Method for recovering crystal from sludge |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3931305A (en) * | 1973-08-20 | 1976-01-06 | Standard Oil Company | Terephthalic acid recovery by continuous flash crystallization |
-
2003
- 2003-12-22 CN CNB2003801085581A patent/CN100453517C/en not_active Expired - Lifetime
- 2003-12-22 WO PCT/JP2003/016465 patent/WO2004063135A1/en active Application Filing
- 2003-12-22 AU AU2003292740A patent/AU2003292740A1/en not_active Abandoned
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064675A (en) * | 1991-02-05 | 1992-09-23 | 帝国化学工业公司 | The preparation method of terephthalic acid |
| JPH09295957A (en) * | 1996-05-07 | 1997-11-18 | Tsukishima Kikai Co Ltd | Production of high-purity aromatic dicarboxylic acid and apparatus therefor |
| CN1278239A (en) * | 1997-10-31 | 2000-12-27 | Hfm国际公司 | Method and apparatus for preparing purified terephthalic acid |
| CN1335296A (en) * | 2000-07-05 | 2002-02-13 | 三菱瓦斯化学株式会社 | Method for recovering crystal from sludge |
Non-Patent Citations (2)
| Title |
|---|
| 三井油化公司PTA工艺技术进展. 赵世民.合成纤维工业，第24卷第5期. 2001 |
| 三井油化公司PTA工艺技术进展. 赵世民.合成纤维工业，第24卷第5期. 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1735581A (en) | 2006-02-15 |
| AU2003292740A1 (en) | 2004-08-10 |
| WO2004063135A1 (en) | 2004-07-29 |
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