WO2004060848A1 - 粗テレフタル酸溶解液の反応器への供給方法 - Google Patents
粗テレフタル酸溶解液の反応器への供給方法 Download PDFInfo
- Publication number
- WO2004060848A1 WO2004060848A1 PCT/JP2003/015685 JP0315685W WO2004060848A1 WO 2004060848 A1 WO2004060848 A1 WO 2004060848A1 JP 0315685 W JP0315685 W JP 0315685W WO 2004060848 A1 WO2004060848 A1 WO 2004060848A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- terephthalic acid
- reactor
- crude terephthalic
- acid solution
- crude
- Prior art date
Links
Classifications
-
- 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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
- B01J8/025—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical in a cylindrical shaped bed
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0278—Feeding reactive fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00548—Flow
Definitions
- the present invention relates to a method for supplying a crude terephthalic acid solution into a reactor in a process for producing high-purity terephthalic acid.
- terephthalic acid which is a raw material for polyester
- paraxylene is dissolved in an acetic acid solvent and oxidized to produce crude terephthalic acid crystals.
- the crude terephthalic acid is refined by passing through a packed tower reactor having a catalyst layer containing a platinum group metal under a hydrogenation reaction treatment in the reactor to obtain high-purity terephthalic acid.
- hydrogen is supplied to the packed column reactor at a pressure equal to or higher than the reaction pressure, and a high-temperature / high-pressure aqueous terephthalic acid solution is supplied.
- a retention zone 4 partitioned by a cylindrical overflow wall 3 is provided at the upper part of a packed tower reactor 11, and a crude terephthalic acid aqueous solution supply port 12 is provided in the retention zone 4. And overflows the cylindrical overflow wall 3 so that only the liquid in which the terephthalic acid crystals are completely dissolved passes through the catalyst layer 2 (for example, , Patent Document 1).
- Reference numeral 5 in the figure denotes a hydrogen supply pipe connection port.
- Patent Document 1 Patent No. 3232700 (Claims)
- Patent Document 2 Patent No. 3232700 (Claims)
- an object of the present invention is to solve the above-mentioned problems, and when a crude terephthalic acid aqueous solution is supplied to a reactor, local wall thinning or destruction occurs on the inner wall surface of the reactor. It is to avoid this.
- crude terephthalic acid obtained by oxidizing para-xylene in an acetic acid solvent is dissolved in water, and this liquid is reduced with hydrogen in the presence of a catalyst in a reactor.
- the method includes the step of supplying the crude terephthalic acid solution into the reactor. It is a method of supplying a crude terephthalic acid solution into a reactor in a production process of high-purity terephthalic acid, characterized in that the inflow velocity is 1 m / s or less.
- the crude terephthalic acid solution is supplied to the inner wall surface of the reactor at a speed of 1 m / s or less. Because of the contact, the burden on the inner wall of the reactor due to the liquid pressure and liquid flow of the crude terephthalic acid solution, which is usually heated to 230 ° C or higher, is reduced, and the reaction by so-called erosion / coagulation is performed. Local thinning or destruction of the inner wall of the vessel is less likely to occur.
- a dispersing device for a liquid flow is provided in the reactor to reduce the inflow rate of the crude terephthalic acid solution, and the crude terephthalic acid solution obtained by the above-described manufacturing process is reduced. It is preferable to use a method of supplying the reactor into the reactor, whereby the burden on the inner wall surface of the reactor is surely reduced.
- the dispersing apparatus has a supply port to which a supply pipe for the crude terephthalic acid solution is connected, and a plurality of dispersion ports opened in the reactor, wherein the area S of the supply port and the plurality of dispersion ports are provided.
- the method is a method of supplying a crude terephthalic acid solution, which is a dispersing device designed to have a ratio to the total area S A of the mouth (S A / S) exceeding 1, into the reactor.
- a dispersing device in which a supply pipe is connected to an annular pipe and a large number of dispersing ports are formed by penetrating the peripheral wall surface of the annular pipe may be adopted.
- the crude terephthalic acid solution can be supplied from the peripheral wall surface of the annular tube to various directions on the inner wall of the reactor, At this time, the inflow pressure can be dispersed and supplied at a low inflow speed.
- the supply of the crude terephthalic acid solution in the production process of high-purity terephthalic acid is such that the flow rate into the reactor is 1 m / s or less.
- the load on the inner wall of the reactor due to the liquid pressure and flow of the high temperature crude terephthalic acid solution above 30 is reduced, and local wall thinning or destruction phenomena on the inner wall of the reactor are less likely to occur. There is an advantage that it becomes.
- the above-described effect can be more reliably achieved by providing a liquid flow dispersing device in the reactor to reduce the inflow rate of the crude terephthalic acid solution.
- a dispersing device for the liquid flow is provided in the reactor to reduce the inflow rate of the crude terephthalic acid solution, and the ratio of the area S of the supply port of the dispersing apparatus to the total area S A of the plurality of dispersing ports ( By designing S A / S) to exceed 1, the burden on the inner wall of the reactor is surely reduced.
- FIG. 1 is a schematic diagram illustrating the structure of the reactor of the embodiment
- FIG. 2 is a longitudinal sectional view showing the upper structure of the reactor of the embodiment
- FIG. 3 is a sectional view taken along line III-III of FIG. 2
- FIG. 5 is a schematic view illustrating the structure of a conventional reactor
- FIG. 5 is a cross-sectional view illustrating the upper structure of a reactor according to another embodiment
- FIG. 6 is a cross-sectional view illustrating the upper structure of another conventional reactor. It is. BEST MODE FOR CARRYING OUT THE INVENTION
- crude terephthalic acid obtained by oxidizing para-xylene in a liquid phase is dissolved in water, and this crude terephthalic acid aqueous solution is subjected to a catalyst in a reactor 1 under high temperature and high pressure. It is passed through layer 2 and reduced with hydrogen.
- the crude terephthalic acid solution is supplied at a flow rate of 1 m / s or less into the reactor 1 in the production process of high-purity terephthalic acid for crystallizing and solid-liquid separation of the reduced product.
- Preferred flow The entry speed is 0.8 SmZs or less, and the more preferred entry speed is 0.8 m / s.
- the lower limit of the flow velocity is preferably 0.1 s, and more preferably 0.2 m / s.
- the oxidation reaction of para-xylene is usually carried out by reacting para-xylene in an acetic acid solvent, for example, in the presence of a catalyst containing cobalt, manganese and bromine, under a temperature condition of usually 170 to 230 molecular oxygen. So-called SD method.
- the crude terephthalic acid obtained by this reaction has a crystallinity generally containing 100 ppm to 50,000 ppm by weight of 40% lipoxybenzaldehyde (hereinafter referred to as “4 CBA”) as an impurity. belongs to.
- Terephthalic acid has low solubility at normal temperature and pressure, and it is necessary to increase the temperature and pressure to increase the solubility of terephthalic acid.
- the following methods are generally used to obtain an aqueous solution of crude terephthalic acid. Can be illustrated.
- crude terephthalic acid is mixed with water at a ratio of 10 to 40% by weight to form a slurry.
- this slurry is pressurized to the reaction pressure plus ⁇ pressure (plus is the pressure taking into account the pressure loss until it reaches the reactor) by a pressurizing pump, and heating is performed using a multi-tube heat exchanger. Supply to dissolution process.
- the temperature increase by heating is carried out in stages up to a predetermined reaction temperature, preferably by a plurality of heat exchanger groups, and the temperature of the crude terephthalic acid solution becomes 230 ° C. or higher.
- the crude terephthalic acid aqueous solution obtained as described above is passed through a packed tower-type reactor 1 in which a catalyst layer 2 containing a platinum group metal is contained. Purify terephthalic acid. Here, 4 CBA in the crude terephthalic acid aqueous solution is reduced to p-toluic acid with hydrogen.
- the catalyst containing a platinum group metal is selected from palladium, ruthenium, rhodium, osmium, iridium, platinum and the like, or a metal oxide thereof. These metals or metal oxides can be used as such as catalysts, but those supported on a carrier such as activated carbon at about 0.2 to 10% by weight are particularly effective.
- the temperature as the reaction condition is from 200 to 400 ° C., preferably from 230 to 350 ° C.
- the pressure only needs to be a pressure that can be maintained as a liquid, and is 1.6 MPa or more. Preferably it is 2.8-16.5 MPa. Hydrogen is supplied to the reactor at a pressure higher than the reaction pressure.
- the packed tower type reactor 1 of the embodiment has a retention zone 4 of a crude terephthalic acid aqueous solution partitioned by an overflow wall 3 at an upper inlet portion.
- This is a structure having a catalyst layer 2 serving as a reaction zone below the retention zone 4.
- the inlet portion at the top of the packed tower type reactor 1 will be described in detail.
- the dome-shaped upper space of the reactor 1 having the hydrogen supply pipe connection port 5 at the top is The stagnation zone 4 and the reaction zone 10 below the stagnation zone 4 are partitioned by a disk-shaped partition plate 6, and a cylindrical overflow wall 3 stands upright in the center of the partition plate 6.
- a crude terephthalic acid solution supply pipe 7 penetrates the side wall of the retention zone 4 and is connected to the annular pipe 8 of the dispersion device.
- the annular pipe 8 is shown as having a cylindrical pipe formed by penetrating a number of small holes 9 in the peripheral wall of the pipe, but other shapes such as cylindrical or polygonal pipes are connected in a polygonal shape. It may be a known ring shape.
- the ratio (S A / S) of the area S of the inner diameter of the supply pipe 7 to the total area SA of the plurality of small holes 9 of the annular pipe 8 is designed to exceed 1, whereby the supply pipe
- the flow rate of the crude terephthalic acid solution in step 7 is 1.1 m / s or more
- the flow rate flowing out of the small hole 9 is designed to be lm / s or less.
- a preferred value of SA / S is 1.1 or more, and a more preferred value is 1.5 or more.
- the upper limit of the S A / S is 1 0 by weight, more preferably 5.
- the solution supplied into the retention zone 4 rises along the overflow wall 3 and finally overflows and is supplied to the reaction zone 10 below the partition plate 6. Is done. At this time, even if there are undissolved crystal particles, the particles settle to the lower part of the retention zone 4 and stay there, and are mixed and dissolved by the solution flow supplied thereto, and do not overflow as they are.
- the flow rate of the crude terephthalic acid solution flowing out of the small holes 9 of the annular pipe 8 is 1 m / s or less, and the overflow terephthalic acid solution contacts the overflow wall 3 and the upper side wall of the reactor 1 at the flow rate or less. Therefore, the burden on the inner wall surface of the reactor due to the liquid pressure and the flow of the high-temperature crude terephthalic acid solution is reduced, and local wall thinning or destruction of the inner wall surface of the reactor 1 is unlikely to occur.
- the terephthalic acid solution normally overflowed in this way is purified through the reaction zone 10, specifically, through the catalyst layer 2, and flows out of the system from the lower outlet of the reactor.
- This effluent is usually recovered through further crystallization, solid-liquid separation and drying steps as purified terephthalic acid crystals.
- the crude terephthalic acid as a raw material was converted into a slurry having a concentration of 30% by weight in an aqueous solution, the pressure was raised to 9 MPa, and the temperature was raised to 285 ° C by a multitubular heat exchanger. Shown in 3
- the solution was supplied to a packed tower-type solution supply pipe having a soot structure.
- the reactor has a tower diameter of 1.26 m, a height of 10 m, and a catalyst bed height of 7 m.
- the structure of the retention zone consists of an overflow wall height of 0.7 m and a downcomer diameter of 0.3. m.
- the material of the reactor body is a clad steel in which SUS304 of 7 mm is laminated on carbon steel, and the material of the overflow wall is titanium steel.
- the hydrogen gas was supplied while being dispersed to the stagnation zone, and the hydrogen gas was supplied to the reaction zone from the space inside by overflowing.
- the reaction conditions were a pressure of 8.0 MPa, a temperature of 285 ° C, a hydrogen partial pressure of 0.8 MPa, and 0.5% palladium Z carbon as a catalyst.
- the crude terephthalic acid solution was supplied at about 0.7 m / s to the retention zone at the top of the reactor.
- Example 1 the crude terephthalic acid solution was supplied from the solution supply port to the reactor at 1.1 m / s from the tangential direction without using the annular pipe of the dispersing apparatus as shown in FIG. A hydrogenation reaction was performed in the same manner except for the above.
- the hydrogenation reaction was carried out in the same manner as in Comparative Example 2, except that the material of the reactor was changed to carbon steel and clad steel in which 3 US304 of 5111111 and 2 mm of titanium were laminated in this order.
- the material of the reactor was changed to carbon steel and clad steel in which 3 US304 of 5111111 and 2 mm of titanium were laminated in this order.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003289298A AU2003289298A1 (en) | 2002-12-09 | 2003-12-08 | Method of feeding solution of crude terephthalic acid to reactor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002356889 | 2002-12-09 | ||
JP2002-356889 | 2002-12-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004060848A1 true WO2004060848A1 (ja) | 2004-07-22 |
Family
ID=32708081
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/015685 WO2004060848A1 (ja) | 2002-12-09 | 2003-12-08 | 粗テレフタル酸溶解液の反応器への供給方法 |
Country Status (4)
Country | Link |
---|---|
KR (1) | KR100982367B1 (ja) |
CN (1) | CN1318371C (ja) |
AU (1) | AU2003289298A1 (ja) |
WO (1) | WO2004060848A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014072686A1 (en) * | 2012-11-06 | 2014-05-15 | Johnson Matthey Davy Technologies Limited | Apparatus and process for purification of aromatic carboxylic acid |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2271568A (en) * | 1992-10-13 | 1994-04-20 | Mitsubishi Chem Ind | Process for producing highly pure terephthalic acid |
JPH0769975A (ja) * | 1993-08-27 | 1995-03-14 | Mitsubishi Chem Corp | 高純度テレフタル酸の製造方法 |
JPH10316613A (ja) * | 1997-05-20 | 1998-12-02 | Hitachi Ltd | 芳香族ポリカルボン酸の精製方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3232700B2 (ja) * | 1992-10-13 | 2001-11-26 | 三菱化学株式会社 | 高純度テレフタル酸の製造方法 |
-
2003
- 2003-12-08 WO PCT/JP2003/015685 patent/WO2004060848A1/ja active Application Filing
- 2003-12-08 KR KR1020057009851A patent/KR100982367B1/ko active IP Right Grant
- 2003-12-08 AU AU2003289298A patent/AU2003289298A1/en not_active Abandoned
- 2003-12-08 CN CNB2003801053985A patent/CN1318371C/zh not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2271568A (en) * | 1992-10-13 | 1994-04-20 | Mitsubishi Chem Ind | Process for producing highly pure terephthalic acid |
JPH0769975A (ja) * | 1993-08-27 | 1995-03-14 | Mitsubishi Chem Corp | 高純度テレフタル酸の製造方法 |
JPH10316613A (ja) * | 1997-05-20 | 1998-12-02 | Hitachi Ltd | 芳香族ポリカルボン酸の精製方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014072686A1 (en) * | 2012-11-06 | 2014-05-15 | Johnson Matthey Davy Technologies Limited | Apparatus and process for purification of aromatic carboxylic acid |
GB2524397A (en) * | 2012-11-06 | 2015-09-23 | Johnson Matthey Davy Technologies Ltd | Apparatus and process for purification of aromatic carboxylic acid |
US9302973B2 (en) | 2012-11-06 | 2016-04-05 | Johnson Matthey Davy Technologies Limited | Apparatus and process for purification of aromatic carboxylic acid |
Also Published As
Publication number | Publication date |
---|---|
CN1723186A (zh) | 2006-01-18 |
KR20050095585A (ko) | 2005-09-29 |
CN1318371C (zh) | 2007-05-30 |
KR100982367B1 (ko) | 2010-09-14 |
AU2003289298A1 (en) | 2004-07-29 |
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