CN100581644C - Catalyst filling method - Google Patents
Catalyst filling method Download PDFInfo
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- CN100581644C CN100581644C CN200480000581A CN200480000581A CN100581644C CN 100581644 C CN100581644 C CN 100581644C CN 200480000581 A CN200480000581 A CN 200480000581A CN 200480000581 A CN200480000581 A CN 200480000581A CN 100581644 C CN100581644 C CN 100581644C
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- catalyst
- reaction tube
- helical form
- form object
- diameter
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- 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
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- 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
- B01J8/06—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 in tube reactors; the solid particles being arranged in tubes
-
- 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
- B01J2208/00743—Feeding or discharging of solids
- B01J2208/00769—Details of feeding or discharging
- B01J2208/00778—Kinetic energy reducing devices in the flow channel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A catalyst filling method capable of minimizing the cracking and powdering of catalysts with a rather low mechanical strength and enabling an efficient working, comprising a step of filling the catalysts in a cylindrical reaction tube by inserting spiral objects which meet the requirements of items (1) to (3) below into the reaction tube. Requirements of spiral objects (1) The spiral objects shall be formed by processing linear or plate-like material. The thickness of the linear material or the width of the plate-like material shall be smaller than a value obtained by multiplying the inner diameter of the reaction tube by 0.2. (2) The outer diameter of the spiral objects shall be smaller than the inner diameter of the reaction tube and larger than a value obtained by multiplying the inner diameter of the reaction tube by 0.8, and a value obtained by deducting the outer diameter of the spiral objects from the inner diameter of the reaction tube shall be smaller than any of the diameter, width, depth, and height of the filled catalysts. (3) A pitch formed by the spiral of the spiral objects shall come within the range of 1 to 8 times the inner diameter of the reaction tube, and the spiral shall always be positioned in the same direction.
Description
Technical field
The present invention relates to the method for in erect type reaction tube filling molding catalyst or carried catalyst, in detail, relate to when the time, reduce the breakage of catalyst on the one hand, effectively implement the method for filling operation on the one hand from reaction tube top filler particles shape preformed catalyst or carried catalyst.
Background technology
Described preformed catalyst or carried catalyst (below, be called catalyst) are filled in the method in the reaction tube that is set to vertical direction, the simplest is exactly that catalyst granules is freely fallen from the top of reaction tube.But catalyst is subjected to very big bump when falling, and the ratio that catalyst is physically broken (broken, powdered) increases.This just makes the uniformity of catalyst packed density descend.
Catalyst filling in the reaction tube wishes that uniformity is high more good more.For example, making in acrylic acid oxidation reactor by the gaseous oxidation of propane, propylene or methacrylaldehyde, according to the packed density difference of catalyst, deviation also takes place in the air-flow in the reaction tube.These combine with influences of damaged catalyst, and increase, the catalytic performance that produces the reduction of reaction yield for example or accessory substance reduces or shorten service life of catalyst etc. and be not preferred problem.
The mechanical strength of catalyst can be improved to a certain extent by forming operation or the load operation that changes catalyst.But, so obtain the catalyst that mechanical strength improves, in general, when reaction, effectively specific area or reactivity point reduce, again owing to the distribution that is difficult to the control pore, so the problem that also exists the purpose product yield to reduce.
The method of breakage is opened flat 9-141084 communique the spy and was disclosed before catalyst filling, the method for filling liquid shape thing in reaction tube when preventing that catalyst from filling.Also have, open in the flat 10-277831 communique the spy and disclosed before catalyst filling the method for filling dry ice.But, after catalyst is filled, time-consuming or also must adjust operating environment or the like according to handled material this is the good method that meets industrial needs hardly.
In the public clear 52-6101 communique of spy, the catalyst fill method that inserts and hang down the wire steel of making arbitrary shape from the upper end of reaction tube is disclosed.Also have, the spy opens in the flat 5-31351 communique, gets involved the method for at least one banded material when disclosing catalyst filling.These methods all are to contact the effect that reduces speed of fall by the catalyst that utilization falls with wire steel or banded material.But, the catalyst speed of fall because of the contact between free-falling acceleration and the wire steel/banded material constantly slow down cause discontinuous, and the speed of each catalyst granules is also inequality, increase insert, the speed of fall of catalyst descends more, easy more obstruction, the problem of bringing padding efficient to reduce of causing.
Summary of the invention
The object of the present invention is to provide a kind of fragmentation or powdered to be suppressed to minimum the not high catalyst of mechanical strength, and the catalyst fill method that can effectively operate.
In order to reach purpose of the present invention, the inventor etc. have carried out found that of various researchs, when falling filling in the reaction tube that catalyst is being set to vertical direction, by the helical form object with specific size is inserted in the reaction tube, the track of the catalyst that is filled becomes helical form along reaction tube, can reduce the breakage when filling, and be difficult for causing obstruction.
That is, the present invention reaches above-mentioned purpose of the present invention according to following proposal.
1. when moulding catalyst or carried catalyst are filled in the cylindric reaction tube of being arranged to vertical direction, at inner helical form object and the catalyst filling that satisfies following (1)-(3) condition that insert of this reaction tube,
The condition of described helical form object is:
(1) the helical form object forms by processing wire material or tabular material, and the thickness of this wire material or the width of this tabular material are littler than 0.2 times value of tube inner diameter;
(2) external diameter of helical form object is littler than the internal diameter of reaction tube, 0.8 times value than tube inner diameter is big, and compare any one of diameter, width, the degree of depth and height of the catalyst of being filled from the resulting value of external diameter that tube inner diameter deducts the helical form object all little;
(3) in 1～8 times scope, helical rotation is generally same direction to the pitch of formation spiral with respect to the internal diameter of reaction tube.
2. as the fill method of catalyst as described in above-mentioned 1, it is characterized in that cylindric reaction tube is the reaction tube of multi-tubular reactor;
3. as the fill method of catalyst as described in above-mentioned 1 or 2, it is characterized in that described preformed catalyst or carried catalyst are employed catalyst in the gas phase oxidation.
The specific embodiment
In the present invention, the described cylindric reaction tube that is set to vertical direction is, filled the catalyst of the filling fixed bed type reactor of using on the general industry, and the reaction tube cylindraceous that reacts.
The helical form object that the present invention is used has the effect that falls according to helical trajectory from the catalyst of reaction tube upper end filling that makes in reaction tube.
The helical form object processes by wire material or tabular material, and the thickness of this wire material or the width of tabular material are than 0.2 times the value little (condition 1) of tube inner diameter.
That is, the live width of helical form object is littler than 0.2 times value of tube inner diameter.When surpassing the live width more than this numerical value, catalyst taking place on the helical form object be detained, causes obstruction easily.
When the excesssive gap of helical form object and reaction tube, catalyst falls from here, and perhaps catalyst is clamped herein, and the screw of catalyst is suppressed, and is undesirable therefore.That is to say, the external diameter of helical form object is bigger than 0.8 times value of tube inner diameter, and compares diameter, width, the degree of depth and the height of the catalyst of being filled any one all little (condition 2) from the resulting value of external diameter that the internal diameter of reaction tube deducts the helical form object.The diameter of catalyst, width, the degree of depth and highly be the size of expression catalyst size when catalyst be spherical or when ellipse or shape similarly, then adopt diameter.When being oval, the minor axis of the ellipse of the arbitrary section by the center is equivalent to diameter.When catalyst is cylindric or during similarly shape, then adopt diameter and height.When catalyst is cuboid or shape similarly, then adopt width, the degree of depth and height.
Because the helical form object that inserts is that to be used to strengthen the catalyst of being filled for the helical movement, so its pitch should be in particular 1～8 times (condition 3) of tube inner diameter in suitable scope.If pitch is too short, then catalyst is stuck on the helical form object, causes obstruction easily, if pitch is long, then catalyst increases at the speed of fall of vertical direction, and the damaged degree of catalyst increases, and is undesirable.
The helical form object that inserts reaction tube both can be a continuous solid, also can be the object that is split into several.The position of being inserted from the lower end of reaction tube to any position of upper end all can, in addition, also can to a plurality of certain limits, insert at one.
The rotation direction left-right rotation of the spiral of the helical form object that form to insert all can, in being inserted into the helical form object of same reaction tube, preferably all rotation directions are all identical.When the midway despun words of helical rotation direction at reaction tube, the catalyst motion that falls then becomes discontinuous, and the catalyst of its below is difficult to move along the hand of spiral thus.
The helical form object can remain in the reaction tube jointly with the catalyst of filling, and in addition, when catalyst filling, increases successively by the loading that makes catalyst, and when the catalyst filling in the reaction tube finished, the helical form object can not remain in the reaction tube yet.After catalyst was filled, when relic coil shape object in reaction tube, the material that constitutes this object must be under the reaction condition that adopts the catalyst of having filled, physically, chemically stable, and the material that catalytic reaction is had no adverse effects.
During catalyst filling, wish that the helical form object does not move in fact at above-below direction.This is because the screw of the catalyst that the inhibition that moves up and down of helical form object falls.
Embodiment
According to embodiment the present invention is described below.
Embodiment 1
(a) manufacturing of catalyst
In the presence of molecular oxygen, making and making acrolein oxidation is acrylic acid following catalyst (opening flat 12-169420 communique with reference to the spy).
Alkaline carbonic acid nickel (NiCO
32Ni (OH)
24H
2O) 228g (wherein, use is scaled the amount of the alkaline carbonic acid nickel of moisture content 76%) be scattered among the pure water 300ml, add 50g silica (カ one Off レ Star Network ス #67 is made in (the シ オ ノ ギ) pharmacy (strain) of the wild justice of salt) and 150g antimony trioxide again, fully stir.Heating concentrates this slurry liquid and dry.Then, the individual body and function Muffle furnace that obtains in 800 ℃ of calcinings 3 hours, with its pulverizing, is made the following sizes of 60 orders or 60 orders (oxide powder of Sb-Ni-Si-O).
Pure water 540ml is heated to about 80 ℃, add ammonium paramolybdate 63.9g, ammonium metavanadate 8.4g, niobium hydroxide 4.6g, plumbi nitras 10.2g and copper sulphate 21.2g while stirring successively and make it dissolving, then, the powder of above-mentioned Sb-Ni-Si-O is added in this solution, fully mix.At 80～100 ℃ this slurry heating is concentrated, and pulverize this drying thing, make the following size of 24 orders or 24 orders, add and mix the graphite of 1.5 weight %.Then, be shaped to small-sized compression molding machine
Use Muffle furnace in 400 ℃ of calcinings 5 hours it, obtain catalyst.The atomic ratio that this catalyst is formed is as follows.
Mo∶V∶Nb∶Sb∶Pb∶Ni∶Cu∶Si＝35∶7∶3∶100∶3∶43∶9∶80
(b) fill evaluating apparatus
(vertical fixing of internal diameter 27mm * 2m), the lower end is with the sealing of allyl resin plate water white transparency acrylic resin sebific duct.Be inserted into the interior place, bottom surface that touches up to the lower end of this pipe being processed into the helical form object that thickness is the steel wire making of 3mm (external diameter 25mm, pitch 100mm, height 1.8m).
With 10 ° the state of tilting funnel (ロ one ト) is set on the top of sebific duct, herein the catalyst with previous method manufacturing being filled into the packed layer height is 1m.The catalyst of being filled by funnel can freely not fall at the sebific duct core, and falls along the steel wire helical trajectory.
Behind the catalyst end-of-fill, sebific duct is removed and make it to tilt from fixed station, bottom plate is taken out, extract catalyst lightly out.The catalyst of extracting out again from remaining catalyst, separates broken thing with 7.5 purpose sieve separated powders, and the volume of broken thing is below 2/3 or 2/3.Powder weight to the part by weight of the ratio of filling used whole catalyst weights and broken thing respectively as pulverization rate and percentage of damage and obtain.The pulverization rate of this moment is 0.2%, and percentage of damage is 1.0%.
Comparative example 1
With embodiment 1 same operation, just the helical form object does not insert sebific duct and carries out the filling of catalyst.Catalyst can not be trapped in the sebific duct, but vertically falls.The pulverization rate of this moment is 2.6%, and percentage of damage is 8.2%.
Comparative example 2
With embodiment 1 same operation, just the external diameter of the helix shape that inserts is changed to 20mm, pitch changes to the filling that 120mm carries out catalyst.The catalyst that falls is irregular track.In the catalyst filling operating process, stop up for 3 times, temporarily stop this moment filling, move up and down by making the helical form object, catalyst is fallen.The pulverization rate of this moment is 0.8%, and rupture rate is 3.5%.
Comparative example 3
With embodiment 1 same operation, the helical form object that just adopts the spiral of the helical form object that inserts to have the despun shape of every 60cm carries out the filling of catalyst.At pipe 60cm place, top, catalyst falls along spiral, thereunder falls with irregular track.At the 60cm place of foot, a part of catalyst is the track of spiral, but other then is irregular falling.The pulverization rate of this moment is 0.7%, and rupture rate is 3.1%.
Explain the present invention with reference to specific implementations of the present invention, to those skilled in the art, all can do change miscellaneous or correction without departing from the spirit and scope of the present invention.
The application proposes based on the Japanese application for a patent for invention (the special 2003-416472 of hope) of application on December 15th, 2003, so the content of this application is listed among the present invention as a reference.
Industrial applicibility
According to method of the present invention, when the moulding catalysis at orthostatic reaction pipe top filler particles shape When agent or carried catalyst, reduce on the one hand the breakage of catalyst, can prevent from the one hand stopping up, Therefore, when making catalyst, not only relax the restriction that the physical strength by catalyst brings, and And its operating efficiency can improve greatly during catalyst filling.
Claims (3)
1. the fill method of a catalyst, it is characterized in that, when moulding catalyst or carried catalyst are filled in the cylindric reaction tube of being arranged to vertical direction, at inner helical form object and the catalyst filling that satisfies following (1)-(3) condition that insert of this cylindric reaction tube
The condition of described helical form object is:
(1) the helical form object forms by processing wire material or tabular material, and the thickness of this wire material or the width of this tabular material are littler than 0.2 times value of tube inner diameter;
(2) external diameter of helical form object is littler than the internal diameter of reaction tube, and 0.8 times value than tube inner diameter is big, and compare any one of diameter, width, the degree of depth and height of the catalyst of being filled from the resulting value of external diameter that tube inner diameter deducts the helical form object all little;
(3) pitch that forms spiral is 1～8 times a scope with respect to the internal diameter of reaction tube, and helical rotation is same direction.
2. the fill method of catalyst according to claim 1 is characterized in that cylindric reaction tube is the reaction tube of multi-tubular reactor.
3. the fill method of catalyst as claimed in claim 1 or 2 is characterized in that described preformed catalyst or carried catalyst are employed catalyst in the gas phase oxidation.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003416472A JP4529435B2 (en) | 2003-12-15 | 2003-12-15 | Catalyst filling method |
| JP416472/2003 | 2003-12-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1697688A CN1697688A (en) | 2005-11-16 |
| CN100581644C true CN100581644C (en) | 2010-01-20 |
Family
ID=34696997
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200480000581A Active CN100581644C (en) | 2003-12-15 | 2004-10-20 | Catalyst filling method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4529435B2 (en) |
| CN (1) | CN100581644C (en) |
| WO (1) | WO2005058475A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2996783B1 (en) * | 2012-10-17 | 2014-11-21 | IFP Energies Nouvelles | CATALYST DENSE LOADING SYSTEM IN BAIONNETTE TUBES FOR VAPOREFORMING EXCHANGER REACTOR USING REMOVABLE HELICOIDAL ELEMENTS |
| JP6092421B2 (en) * | 2013-11-07 | 2017-03-08 | 株式会社日本触媒 | Packing for reaction tube, reaction tube, and reaction method using the same |
| CN113631255A (en) | 2019-03-29 | 2021-11-09 | 三菱化学株式会社 | Method for filling granular material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS523579A (en) * | 1975-06-27 | 1977-01-12 | Sumitomo Chem Co Ltd | Method of packing |
| JPH0545394A (en) * | 1991-08-09 | 1993-02-23 | Fujitsu Ltd | Testing device of hysteresis comparator |
| JPH067669A (en) * | 1992-06-26 | 1994-01-18 | Mitsubishi Rayon Co Ltd | Packing method of catalyst for synthesizing acrolein and acrylic acid |
| EP1283070B1 (en) * | 2001-08-07 | 2004-06-02 | Haldor Topsoe A/S | Catalyst loading method and apparatus |
-
2003
- 2003-12-15 JP JP2003416472A patent/JP4529435B2/en not_active Expired - Lifetime
-
2004
- 2004-10-20 WO PCT/JP2004/015858 patent/WO2005058475A1/en active Application Filing
- 2004-10-20 CN CN200480000581A patent/CN100581644C/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005169345A (en) | 2005-06-30 |
| JP4529435B2 (en) | 2010-08-25 |
| CN1697688A (en) | 2005-11-16 |
| WO2005058475A1 (en) | 2005-06-30 |
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Address after: Tokyo, Japan Patentee after: MITSUBISHI CHEMICAL Corp. Address before: Tokyo, Japan Patentee before: MITSUBISHI RAYON Co.,Ltd. |
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Effective date of registration: 20170905 Address after: Tokyo, Japan Patentee after: MITSUBISHI RAYON Co.,Ltd. Address before: Tokyo, Japan Patentee before: MITSUBISHI CHEMICAL Corp. |
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