CN102134057A - Reactor for preparing chlorine by catalytic oxidation of hydrogen chloride - Google Patents
Reactor for preparing chlorine by catalytic oxidation of hydrogen chloride Download PDFInfo
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- CN102134057A CN102134057A CN 201110023339 CN201110023339A CN102134057A CN 102134057 A CN102134057 A CN 102134057A CN 201110023339 CN201110023339 CN 201110023339 CN 201110023339 A CN201110023339 A CN 201110023339A CN 102134057 A CN102134057 A CN 102134057A
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- metal shell
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- retaining wall
- air retaining
- sublayer
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 30
- 239000000460 chlorine Substances 0.000 title claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 108
- 239000002184 metal Substances 0.000 claims abstract description 108
- 238000009413 insulation Methods 0.000 claims abstract description 65
- 238000005260 corrosion Methods 0.000 claims abstract description 42
- 230000007797 corrosion Effects 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000012429 reaction media Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 13
- 239000004567 concrete Substances 0.000 claims description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000011449 brick Substances 0.000 claims description 22
- 230000004888 barrier function Effects 0.000 claims description 19
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 15
- 239000010962 carbon steel Substances 0.000 claims description 15
- 239000010425 asbestos Substances 0.000 claims description 12
- 229910052895 riebeckite Inorganic materials 0.000 claims description 12
- 229910001220 stainless steel Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 229910045601 alloy Inorganic materials 0.000 claims description 10
- 239000000956 alloy Substances 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 9
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 9
- 239000004927 clay Substances 0.000 claims description 9
- 239000010433 feldspar Substances 0.000 claims description 9
- 239000004571 lime Substances 0.000 claims description 9
- 235000019353 potassium silicate Nutrition 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000011490 mineral wool Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004568 cement Substances 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 239000010431 corundum Substances 0.000 claims description 5
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052863 mullite Inorganic materials 0.000 claims description 5
- 150000003016 phosphoric acids Chemical class 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 239000011491 glass wool Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000005299 abrasion Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 11
- 230000003628 erosive effect Effects 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 238000007138 Deacon process reaction Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052902 vermiculite Inorganic materials 0.000 description 2
- 239000010455 vermiculite Substances 0.000 description 2
- 235000019354 vermiculite Nutrition 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- -1 haydite Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Abstract
The invention discloses a reactor for preparing chlorine by catalytic oxidation of hydrogen chloride. The reactor comprises a reactor wall of a multilayer structure and a reaction chamber limited by the reactor wall and used for accommodating a reaction medium. The reactor is characterized in that: the reactor wall of the multilayer structure comprises a metal shell, an outer heat insulation layer and a lining layer, wherein the outer heat insulation layer is arranged on the outer side of the metal shell and used for insulating the metal shell, and in a working state, the temperature of the outer surface of the metal shell contacted with the outer heat insulation layer is higher than the dew point of water due to the thickness of the outer heat insulation layer; and the lining layer is arranged on the inner side of the metal shell, and in a working state, the temperature of the inner surface of the metal shell is less than 300 DEG C due to the thickness of the lining layer. According to the embodiment of the invention, the reactor wall has the properties of heat insulation, abrasion resistance and corrosion resistance, so the reactor has long service life and low preparation cost.
Description
Technical field
The present invention relates to the chemical industry equipment field, relate in particular to the reactor that a kind of catalytic oxidation of hydrogen chloride for preparing is equipped with chlorine.
Background technology
Many be in the commercial run of raw material with chlorine, for example the MDI/TDI of urethane industry, Mannheim proeess produce vitriolate of tartar, methane chloride, Mono Chloro Acetic Acid and clorafin etc., all can produce a large amount of byproduct hydrogen chlorides.With the urethane industry is example, needs to use chloride COCl in producing MDI, TDI process
2, and not containing chlorine in the product, chlorine all changes into byproduct hydrogen chloride.The MDI device of 100,000 t/a produces the hydrogenchloride of 60,000 t/a approximately, and the TDI device of 100,000 t/a produces the hydrogenchloride of 8.39 ten thousand t/a approximately.If a large amount of byproduct hydrogen chlorides can not get reasonably utilizing, the sound development of related industries will be restricted seriously.Therefore, people wish to find not only an economy but also safe hydrogenchloride preparing chlorine gas operational path, to realize the recycle of chlorine element.
There are a lot of hydrogenchloride to prepare the method for chlorine in the document, mainly contain electrolytic process, inorganic oxidizer direct oxidation method and air/oxygen catalytic oxidation (being the Deacon process).The electrolytic process energy consumption is too big, the cost height; The shortcoming of inorganic oxidizer direct oxidation method is the equipment more complicated, the product separation difficulty, and energy consumption is bigger simultaneously; The Deacon process is that hydrogenchloride and oxygen at 300 ℃～550 ℃ chemical reactions take place under the condition of the oxide compound of Cu, Ru or Cr etc. or chloride catalyst existence, thereby makes the process of chlorine.Reaction formula that it is generally acknowledged the Deacon process is as follows:
Because this process is an exothermic process, needs to be provided with heat transfer tube in reactor.In addition, comprise HCl, Cl in the reaction system of this process
2, H
2O and O
2, under 300 ℃～550 ℃ temperature of reaction, low-cost metal material such as carbon steel can seriously corroded.For this reason, SUMITOMO CHEMICAL chemical company adopts the calandria type fixed bed reactor of nickel material, but the defective that there is processed complex in this equipment, involves great expense.
For enhancement of heat transfer, this reaction process also can adopt fluidized-bed reactor.Advantages such as heat-transfer effect is good though fluidized-bed reactor has, uniformity of temperature profile, and the catalyzer inside diffusional resistance is little, catalyzer is violent to the collision friction of the wall of reactor, thereby quickens the corrosion of metal wall.
Therefore, need develop a kind of reactor, this reactor is equipped with in the process of chlorine at catalytic oxidation of hydrogen chloride for preparing, and the wall of reactor can high temperature resistant, anti-HCl and Cl
2The anti-solid catalyst of burn into of (moisture) wash away abrasion, also have certain mechanical strength simultaneously.
Summary of the invention
The present invention is intended to solve at least one of technical problem that exists in the prior art.
For this reason, the objective of the invention is to propose a kind of high temperature resistant, erosion resistant and corrosion resistant reactor.
To achieve these goals, according to embodiments of the invention a kind of reactor that catalytic oxidation of hydrogen chloride for preparing is equipped with chlorine that is used for is proposed, the wall of reactor that comprises multilayered structure of described reactor, and by the reaction chamber that is used to hold reaction medium that wall limited, the wall of reactor of described multilayered structure comprises: metal shell; External thermal insulation, its outside that is arranged on described metal shell are used for the insulation of described metal shell, and in the time of in working order, the thickness of described external thermal insulation makes the dew point that is higher than water with the contacted metal shell hull-skin temperature of external thermal insulation; And air retaining wall, it is arranged on the inboard of described metal shell, and in the time of in working order, the thickness of described air retaining wall makes the metal shell internal surface temperature be lower than 300 ℃.
Reducing heat according to the reactor of the embodiment of the invention by the arranged outside external thermal insulation at metal shell scatters and disappears, thereby the temperature that makes described metal shell is not less than the dew-point temperature of water, has so just prevented that reaction medium from corroding described metal shell because of forming hydrochloric acid.Described reactor is provided with air retaining wall by the inboard at described metal shell and intercepts reaction medium (comprising solid catalyst), the heat that reduces described reaction medium is passed to described metal shell and avoids described metal shell to be denuded by reaction medium and corrode, thereby has prolonged the work-ing life of described reactor widely.
By external thermal insulation and air retaining wall being set respectively in the outside and inboard according to the metal shell of the reactor of the embodiment of the invention, can prevent that reaction medium (comprising catalyzer) from denuding and corrode described metal shell, thereby can use ordinary metallic material to prepare described metal shell, reduce the preparation cost of described reactor widely.
In addition, the reactor according to the embodiment of the invention can have following additional technical characterictic:
According to one embodiment of present invention, the thickness of described external thermal insulation is satisfied makes the hull-skin temperature of metal shell be higher than 180 ℃.
According to one embodiment of present invention, the thickness of described air retaining wall is satisfied makes the metal shell internal surface be lower than 250 ℃.
According to one embodiment of present invention, described metal shell is made by carbon steel or stainless steel, thereby has reduced the preparation cost of described reactor widely.
According to one embodiment of present invention, described external thermal insulation is made by in mineral wool, rock wool, the anti-heat-insulation blanket of dimension and the glass wool one or more.
According to one embodiment of present invention, described air retaining wall is made of corrosion resistant concrete, and described corrosion resistant concrete comprises aggregate and fine powder, and wherein said aggregate comprises mullite, quartz and lime feldspar, and described fine powder comprises lime feldspar, Dong Changshi and luminite cement.Described air retaining wall can form by the method for deposit concrete is whole, has the easy advantage of preparation.
According to one embodiment of present invention, described air retaining wall comprises heat insulation sublayer and wear resistant corrosion resistant sublayer, and described heat insulation sublayer is adjacent with described metal shell, and described heat insulation sublayer is by the pouring heat insulating concrete material or build insulating brick by laying bricks or stones and constitute; Described wear resistant corrosion resistant sublayer is arranged on inboard, described heat insulation sublayer, described wear resistant corrosion resistant sublayer is formed by the wear resistant corrosion resistant concrete depositing or is built by laying bricks or stones in conjunction with the prefabricated ring of high alumina by silicon carbide brick, corundum brick or phosphoric acid salt and forms, and perhaps is made of nickel or nickel-base alloy.
According to one embodiment of present invention, also be provided with barrier film on the internal surface of described metal shell, it is used to prevent that reaction medium is penetrated into described metal shell, and wherein said barrier film is made of the rare clay of nickel, nickel-base alloy or water glass.
According to one embodiment of present invention, described barrier film is arranged on the internal surface of described metal shell by thermospray.
According to one embodiment of present invention, comprise also that between described metal shell and air retaining wall the asbestos flaggy is used to prevent described metal shell distortion and the be full of cracks of described air retaining wall.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment in conjunction with following accompanying drawing, wherein:
Fig. 1 is the structural representation (part) of reactor according to an embodiment of the invention;
Fig. 2 is the structural representation (part) of reactor according to another embodiment of the invention.
Description of reference numerals:
Embodiment
Describe embodiments of the invention below in detail, the example of described embodiment is shown in the drawings, and wherein identical from start to finish or similar label is represented identical or similar elements or the element with identical or similar functions.Below by the embodiment that is described with reference to the drawings is exemplary, only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, term " vertically ", " laterally ", " on ", close the orientation of indications such as D score, " preceding ", " back ", " left side ", " right side ", " vertically ", " level ", " top ", " end " or position is based on orientation shown in the drawings or position relation, only be the present invention for convenience of description rather than require the present invention therefore can not be interpreted as limitation of the present invention with specific orientation structure and operation.
In addition, term " first ", " second " only are used to describe purpose, and can not be interpreted as indication or hint relative importance.
In description of the invention, unless otherwise prescribed and limit, need to prove, term " installation ", " linking to each other ", " connection " should be done broad understanding, for example, can be mechanical connection or electrical connection, it also can be the connection of two element internals, can be directly to link to each other, also can link to each other indirectly by intermediary, on the equipment between adjacent two devices the contact by process medium also be referred to as " linking to each other " or " connection ".For the ordinary skill in the art, can understand the concrete implication of above-mentioned term as the case may be.
The contriver is containing HCl and Cl by discovering
2In the atmosphere of (moisture), when temperature was higher than the dew point of water, hcl corrosion can not appear in carbon steel and common stainless steel etc.; When temperature is no more than 300 ℃, the main FeCl that generates of Fe and Cl reaction
2, because FeCl
2Fusing point is 576 ℃, 10
-4Boiling point under the normal atmosphere is 536 ℃, makes to have formed one deck FeCl on surfaces such as carbon steel and common stainless steels
2Protective membrane, thus stop corrosion to be proceeded.If temperature surpasses 300 ℃, will make the FeCl that forms from the teeth outwards originally
2Protective membrane further with reaction medium in Cl
2Reaction forms FeCl
3, this moment is because FeCl
3Fusing point is 303 ℃ only, 10
-4Boiling point under the normal atmosphere is 167 ℃ only, makes carbon steel or common stainless steel surface constantly form FeCl
3And evaporate, this makes carbon steel easily because of forming FeCl
3And constantly corroded.
Inventor research is also found, compares with carbon steel, common stainless steel material, and many inorganic materials can be used containing under the high-temperature atmosphere of Cl.Lining material (Wu Mingyou as the fluidizing chlorination furnace apparatus of titanium tetrachloride, the material of ebullated bed chlorination furnace is selected and parameter is determined, coal technology, 2000,19 (1), 57-58), the catalytic cracking of petrochemical industry (FCCU) device (Fang Jiagui etc., the present state and perspectives of catalytic cracking unit lining technology, the petrochemical equipment technology, 2006,27 (4) 7-13), circular fluid bed (Ma Shuqi, the design and construction of circulating fluid bed boiler lining, thermal power engineering, 1993,8 (5), 242-249) etc.But its physical strength of these inorganic materials is limited, can not directly use inorganic materials to make reactor.
Based on above-mentioned research, the invention provides a kind of reactor that is used for catalytic oxidation of hydrogen chloride for preparing chlorine gas.Below with reference to Fig. 1 and Fig. 2 the reactor that catalytic oxidation of hydrogen chloride for preparing is equipped with chlorine that is used for according to the embodiment of the invention is described.As depicted in figs. 1 and 2, according to the reactor of the embodiment of the invention comprise the wall of reactor of multilayered structure, and by the reaction chamber that is used to hold reaction medium that wall limited.The wall of reactor of described multilayered structure comprises metal shell 1, external thermal insulation 2 and air retaining wall 3.The outside that external thermal insulation 2 is arranged on metal shell 1 is used for metal shell 1 insulation, in the time of in working order, the thickness of external thermal insulation 2 makes the temperature with the outside surface of external thermal insulation 2 contacted metal shells 1 be higher than the dew point of water, has so just prevented because of forming hydrochloric acid corroding metal housing 1.Air retaining wall 3 is arranged on the inboard of metal shell 1, and in the time of in working order, the thickness of air retaining wall 3 makes the temperature of internal surface of metal shell 1 be lower than 300 ℃, to avoid metal shell 1 by described reaction medium (particularly solid catalyst) abrasion and corrosion.Wherein, the outside of metal shell 1 is meant a side of the close environment of metal shell 1, and the inboard of metal shell 1 is meant a side of the close reaction medium of metal shell 1.
Reduce heat according to the reactor of the embodiment of the invention by arranged outside external thermal insulation 2 and scatter and disappear, thereby make the temperature of metal shell 1 be not less than the dew-point temperature of water, so just prevented because of forming hydrochloric acid corroding metal housing 1 at metal shell 1.Described reactor is provided with air retaining wall 3 by the inboard at metal shell 1 and intercepts reaction medium (comprising solid catalyst), the heat that reduces described reaction medium is passed to metal shell 1 and avoids metal shell 1 to be denuded by reaction medium and corrode, thereby has prolonged the work-ing life of described reactor widely.
By external thermal insulation 2 and air retaining wall 3 being set respectively in the outside and inboard according to the metal shell 1 of the reactor of the embodiment of the invention, can prevent reaction medium (comprising catalyzer) abrasion and corroding metal housing 1, thereby can use ordinary metallic material to prepare metal shell 1, reduce the preparation cost of described reactor widely.
In an example of the present invention, the thickness of external thermal insulation 2 satisfies makes the hull-skin temperature of metal shell 1 be higher than 180 ℃.In another example of the present invention, the thickness of air retaining wall 3 satisfies makes the internal surface of metal shell 1 be lower than 250 ℃.
In an example of the present invention, metal shell 1 can be made by carbon steel or stainless steel.Containing HCl and Cl
2In the atmosphere of (moisture), when temperature was higher than the dew point of water, hcl corrosion can not appear in carbon steel and common stainless steel etc.; When temperature is no more than 300 ℃ (preferably being no more than 250 ℃), the main FeCl that generates of Fe and Cl reaction
2, FeCl
2Fusing point is 576 ℃, 10
-4Boiling point under the normal atmosphere is 536 ℃, has formed one deck FeCl on surfaces such as carbon steel and common stainless steels
2Protective membrane, thus stop corrosion to be proceeded; As the further raising along with temperature, FeCl
2Can further mainly generate FeCl with the Cl reaction
3, FeCl
3Fusing point is 303 ℃, 10
-4Boiling point under the normal atmosphere is 167 ℃, carbon steel just be corroded easily (be coated with river equality, the corrosion of metal in the high temperature chlorine gas environment, the material Leader, 1993,6,23-26).Therefore, have only when temperature be higher than the dew point of water, when being no more than 300 ℃ (being preferably between 180 ℃ and 250 ℃), carbon steel and common stainless steel etc. can be at HCl and Cl
2Use in the atmosphere of (moisture).And in the reactor of the above embodiment of the present invention, can reduce heat by the arranged outside external thermal insulation 2 at metal shell 1 scatters and disappears, to metal shell 1 insulation, thereby the temperature that makes metal shell 1 is higher than the dew point of water, and air retaining wall 3 is set to prevent in solid catalyst abrasion metal shell 1 and the reaction medium corroding metal housing 1 temperature with metal shell 1 and remain on the dew point that is higher than water and to be no more than in 300 ℃ the scope by inboard at metal shell 1, this just makes and uses carbon steel and stainless steel to become possibility, and carbon steel and stainless steel have cheap advantage, thereby can reduce the preparation cost of metal shell 1 widely, and then reduce preparation cost widely according to the reactor of the embodiment of the invention.
External thermal insulation 2 according to the reactor of the embodiment of the invention can be made by any one material with heat insulation function.In an example of the present invention, external thermal insulation 2 can be made by in mineral wool, dimension anti-heat-insulation blanket and the glass wool one or more.Mineral wool, the anti-heat-insulation blanket of dimension and glass wool have advantage cheap, high insulating effect, and can obtain by the commercial channel.
Have heat insulation, erosion resistant and corrosion resistant performance according to the air retaining wall 3 of the reactor of the embodiment of the invention.Air retaining wall 3 can be formed by concrete depositing, and can make concrete have heat insulation or the corrosion resistant performance of erosion resistant by adjusting concrete composition and proportioning thereof, perhaps has heat insulation simultaneously and the corrosion resistant performance of erosion resistant.Can use the concrete that has heat insulation and erosion resistant corrosion resistance nature simultaneously as air retaining wall 3, the concrete that also can use concrete with heat-proof quality and wear-corrosion resistance is as air retaining wall 3, can also use concrete with erosion resistant corrosion resistance nature and other lagging materials as air retaining wall 3.
In addition, can also adjust air retaining wall 3 according to the different of catalyzer, reaction process and reactor.For example, adopt catalyzer Ru, Cu or Cr, suitable temperature of reaction is about 300 ℃, 400 ℃ or 500 ℃ respectively.Adopt the Ru catalyzer, temperature of reaction is lower, reaches the requirement that the metal shell temperature is no more than 250 ℃ easily, and is lower to the heat insulation requirement of air retaining wall 3; Adopt the Cu catalyzer, temperature of reaction is higher, and is also higher to the heat insulation requirement of air retaining wall 3; Adopt the Cr catalyzer, temperature of reaction is higher, and is also higher to the heat insulation requirement of air retaining wall 3.In addition, adopt the reactor of different types, also different to the wear-resisting requirement of air retaining wall 3.For example, adopt fixed-bed reactor, do not have the problem of granules of catalyst and wall of reactor gouging abrasion, therefore the wear resistance to air retaining wall 3 requires lower; And the employing fluidized-bed reactor, air retaining wall 3 must be wear-resisting.Therefore, those skilled in the art can adjust the heat-proof quality and the wear resisting property of air retaining wall 3 as the case may be adaptively.
In some embodiments of the invention, air retaining wall 3 can be made of corrosion resistant concrete.Described corrosion resistant concrete can comprise aggregate and fine powder, and wherein said aggregate can comprise mullite, quartz and lime feldspar, and described fine powder can comprise lime feldspar, Dong Changshi and luminite cement.That described corrosion resistant concrete has simultaneously is heat insulation, erosion resistant and corrosion resistant performance.Air retaining wall 3 can form by the method for deposit concrete is whole, has the easy advantage of preparation.
In some embodiments of the invention, air retaining wall 3 can comprise heat insulation sublayer 31 and wear resistant corrosion resistant sublayer 32.Heat insulation sublayer 31 is adjacent with metal shell 1, is used to intercept the heat that reaction produces and transmits to metal shell 1.Wear resistant corrosion resistant sublayer 32 can be arranged on the inboard of heat insulation sublayer 31, be used to intercept described reaction medium (comprising solid catalyst), when reacting, wear resistant corrosion resistant sublayer 32 directly contacts with described reaction medium, thereby can avoid solid catalyst abrasion metal shell 1 and described reaction medium corroding metal housing 1.
In some embodiments of the invention, heat insulation sublayer 31 can be formed or be built by laying bricks or stones by insulating brick and form by heat insulating concrete cast.Therefore, heat insulation sublayer 31 not only has heat insulation performance, also has the performance of wear resistant corrosion resistant.Wherein, described heat insulating concrete can comprise aggregate and fine powder.Described aggregate can comprise mullite, quartz, lime feldspar, haydite and vermiculite, and described fine powder can comprise lime feldspar, aluminum oxide, Dong Changshi and luminite cement.Described insulating brick can be known any one insulating brick, and can obtain by the commercial channel.
In some embodiments of the invention, wear resistant corrosion resistant sublayer 32 can be formed by the wear resistant corrosion resistant concrete depositing, is perhaps built by laying bricks or stones in conjunction with the prefabricated ring of high alumina by silicon carbide brick, corundum brick or phosphoric acid salt to form, and perhaps is made of nickel or nickel-base alloy.Silicon carbide brick, corundum brick or phosphoric acid salt can obtain by the commercial channel in conjunction with the prefabricated ring of high alumina.When wear resistant corrosion resistant sublayer 32 is built by laying bricks or stones when forming in conjunction with the prefabricated ring of high alumina by silicon carbide brick, corundum brick or phosphoric acid salt, can be understood as in the inboard of air retaining wall 3 increases a wear resistant corrosion resistant layer, thereby further improves the wear-corrosion resistance according to the reactor of the embodiment of the invention.
According to the reactor of the embodiment of the invention, concrete various compositions, for example mullite, quartz, lime feldspar, haydite, vermiculite, aluminum oxide, Dong Changshi and luminite cement etc. all can obtain by the commercial channel.
In some embodiments of the invention, can also comprise barrier film 4, be used to prevent that described reaction medium is penetrated into metal shell 1 according to the reactor of the embodiment of the invention.Barrier film 4 can be arranged on the internal surface of metal shell 1, and promptly barrier film 4 is between metal shell 1 and air retaining wall 3.By being set, barrier film 4 can prevent that hydrogenchloride, water and chlorine are penetrated into the internal surface of metal shell 1 and then corroding metal housing 1 by air retaining wall 3 on the internal surface of metal shell 1.In an example of the present invention, barrier film 4 can be made of the rare clay of nickel, nickel-base alloy or water glass.The rare clay layer of described water glass can be made by the rare clay of known any one water glass, and the rare clay of described water glass can obtain by the commercial channel.
In a concrete example of the present invention, barrier film 4 can utilize described nickel or nickel-base alloy to be arranged on the internal surface of metal shell 1 by heat spraying method.In another concrete example of the present invention, barrier film 4 can utilize the rare clay of described water glass to be arranged on the internal surface of metal shell 1 by heat spraying method.It will be appreciated by persons skilled in the art that according to concrete reaction process condition, can utilize described nickel and/or nickel-base alloy simultaneously in order to improve impermeable effect, and the rare clay of described water glass.For example, can be by the heat spraying method described nickel of thermospray or nickel-base alloy on the internal surface of metal shell 1, thus can form barrier film 4 by the rare clay of brushing method described water glass of thermospray on described nickel or nickel-base alloy then.
In some embodiments of the invention, can also comprise asbestos flaggy 5 according to the reactor of the embodiment of the invention, asbestos flaggy 5 can be arranged on and be used to prevent that metal shell 1 distortion and air retaining wall 3 from chapping between metal shell 1 and the air retaining wall 3.Can cushion by the different hot swollen differences that cause of metal shell 1 by asbestos flaggy 5 is set between metal shell 1 and air retaining wall 3, thereby prevent metal shell 1 distortion and air retaining wall 3 be full of cracks with the thermal expansion coefficient of air retaining wall 3.Asbestos flaggy 5 can be made by known any one asbestos plate, and described asbestos plate can obtain by the commercial channel.
In one embodiment of the invention, reactor according to the embodiment of the invention can also comprise barrier film 4 and asbestos flaggy 5, barrier film 4 can be arranged on the internal surface of metal shell 1, and between metal shell 1 and air retaining wall 3, asbestos flaggy 5 can be arranged between barrier film 4 and the air retaining wall 3.Can prevent that so not only hydrogenchloride, water and chlorine are penetrated into the internal surface of metal shell 1 by air retaining wall 3, and can prevent metal shell 1 distortion and air retaining wall 3 be full of cracks.
Can determine the thickness of metal shell 1, external thermal insulation 2, air retaining wall 3, barrier film 4 and asbestos flaggy 5 according to concrete working conditions (for example reaction process condition) according to the reactor of the embodiment of the invention.
Have heat insulation, erosion resistant and corrosion resistant performance according to the reactor of the embodiment of the invention, long service life, preparation cost is low.
Produce 20000 tons catalytic oxidation of hydrogen chloride for preparing chlorine gas process per year, adopt fluidized-bed reactor, processing parameter is as follows:
Temperature of reaction: 400 ℃
Absolute pressure: 2.0atm
Charging air speed: 0.25h
-1(in HCl)
Charge ratio: 2: 1 (HCl: O
2)
HCl transformation efficiency: 70%
Catalyzer is that active ingredient is CuCl
2Loaded catalyst, support of the catalyst is Al
2O
3, median size is 50 μ m.
Reactor inside diameter Φ 1750mm, the wall of reactor as shown in Figure 1.The temperature outside of the external thermal insulation 2 of this reactor is 60 ℃, and the temperature of metal shell 1 is 250 ℃.
Example two
Industrial scale is identical with example one with processing condition.
Reactor inside diameter Φ 1750mm, the wall of reactor as shown in Figure 2.The temperature outside of the external thermal insulation 2 of this reactor is 60 ℃, and the temperature of metal shell 1 is 250 ℃.
Example three
Produce 30000 tons catalytic oxidation of hydrogen chloride for preparing chlorine gas process per year, adopt fixed-bed reactor, processing parameter is as follows:
Temperature of reaction: 300 ℃
Absolute pressure: 2.5atm
Charging air speed: 0.5h
-1(in HCl)
Charge ratio: 2: 1 (HCl: O
2)
HCl transformation efficiency: 70%
Catalyzer is that active ingredient is RuCl
2Loaded catalyst, support of the catalyst is Al
2O
3, median size is 3mm.
Reactor inside diameter Φ 2000mm,, the wall of reactor is as shown in Figure 2.The temperature outside of the external thermal insulation 2 of this reactor is 50 ℃, and the temperature of metal shell 1 is 300 ℃.
In the description of this specification sheets, concrete feature, structure, material or characteristics that the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means in conjunction with this embodiment or example description are contained at least one embodiment of the present invention or the example.In this manual, the schematic statement to above-mentioned term not necessarily refers to identical embodiment or example.And concrete feature, structure, material or the characteristics of description can be with the suitable manner combination in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: can carry out multiple variation, modification, replacement and modification to these embodiment under the situation that does not break away from principle of the present invention and aim, scope of the present invention is limited by claim and equivalent thereof.
Claims (10)
1. a catalytic oxidation of hydrogen chloride for preparing is equipped with the reactor of chlorine, it comprise multilayered structure wall of reactor, and, it is characterized in that the wall of reactor of described multilayered structure comprises by the reaction chamber that is used to hold reaction medium that wall limited:
Metal shell;
External thermal insulation, its outside that is arranged on described metal shell are used for the insulation of described metal shell, and in the time of in working order, the thickness of described external thermal insulation makes the dew point that is higher than water with the contacted metal shell hull-skin temperature of external thermal insulation; With
Air retaining wall, it is arranged on the inboard of described metal shell, and in the time of in working order, the thickness of described air retaining wall makes the metal shell internal surface temperature be lower than 300 ℃.
2. reactor according to claim 1 is characterized in that, the thickness of described external thermal insulation satisfies makes the hull-skin temperature of metal shell be higher than 180 ℃.
3. reactor according to claim 1 is characterized in that, the thickness of described air retaining wall satisfies makes the metal shell internal surface be lower than 250 ℃.
4. reactor according to claim 1 is characterized in that described metal shell is made by carbon steel or stainless steel.
5. reactor according to claim 1 is characterized in that, described external thermal insulation is made by in mineral wool, rock wool, the anti-heat-insulation blanket of dimension and the glass wool one or more.
6. reactor according to claim 1, it is characterized in that described air retaining wall is made of corrosion resistant concrete, described corrosion resistant concrete comprises aggregate and fine powder, wherein said aggregate comprises mullite, quartz and lime feldspar, and described fine powder comprises lime feldspar, Dong Changshi and luminite cement.
7. reactor according to claim 1 is characterized in that, described air retaining wall comprises heat insulation sublayer and wear resistant corrosion resistant sublayer,
Described heat insulation sublayer is adjacent with described metal shell, and described heat insulation sublayer is by the pouring heat insulating concrete material or build insulating brick by laying bricks or stones and constitute;
Described wear resistant corrosion resistant sublayer is arranged on inboard, described heat insulation sublayer, described wear resistant corrosion resistant sublayer is formed by the wear resistant corrosion resistant concrete depositing or is built by laying bricks or stones in conjunction with the prefabricated ring of high alumina by silicon carbide brick, corundum brick or phosphoric acid salt and forms, and perhaps is made of nickel or nickel-base alloy.
8. reactor according to claim 1, it is characterized in that, also be provided with barrier film on the internal surface of described metal shell, it is used to prevent that reaction medium is penetrated into described metal shell, and wherein said barrier film is made of the rare clay of nickel, nickel-base alloy or water glass.
9. reactor according to claim 8 is characterized in that described barrier film is arranged on the internal surface of described metal shell by thermospray.
10. reactor according to claim 1 is characterized in that, also comprises the asbestos flaggy between described metal shell and air retaining wall.
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| CN 201110023339 CN102134057B (en) | 2011-01-20 | 2011-01-20 | Reactor for preparing chlorine by catalytic oxidation of hydrogen chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110023339 CN102134057B (en) | 2011-01-20 | 2011-01-20 | Reactor for preparing chlorine by catalytic oxidation of hydrogen chloride |
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| CN102134057B CN102134057B (en) | 2013-01-16 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515264A (en) * | 2011-11-09 | 2012-06-27 | 攀钢集团工程技术有限公司 | Boiling chlorination furnace and manufacturing method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1362212A (en) * | 1970-09-28 | 1974-07-30 | Fmc Corp | Production of chlorinated hydrocarbons |
| US4080435A (en) * | 1973-12-11 | 1978-03-21 | Aluminum Company Of America | Aluminum chloride production process |
| CN1919442A (en) * | 2006-08-01 | 2007-02-28 | 遵义钛业股份有限公司 | Multi-laminar flow cribriform-plate-free boiling chloridization furnace |
-
2011
- 2011-01-20 CN CN 201110023339 patent/CN102134057B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1362212A (en) * | 1970-09-28 | 1974-07-30 | Fmc Corp | Production of chlorinated hydrocarbons |
| US4080435A (en) * | 1973-12-11 | 1978-03-21 | Aluminum Company Of America | Aluminum chloride production process |
| CN1919442A (en) * | 2006-08-01 | 2007-02-28 | 遵义钛业股份有限公司 | Multi-laminar flow cribriform-plate-free boiling chloridization furnace |
Non-Patent Citations (1)
| Title |
|---|
| 《天津冶金》 20090228 孙刘恒等 含氯废塑料脱氯反应器内衬材质研究 , 第1期 2 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102515264A (en) * | 2011-11-09 | 2012-06-27 | 攀钢集团工程技术有限公司 | Boiling chlorination furnace and manufacturing method thereof |
| CN102515264B (en) * | 2011-11-09 | 2014-09-03 | 攀钢集团工程技术有限公司 | Boiling chlorination furnace and manufacturing method thereof |
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| CN102134057B (en) | 2013-01-16 |
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