CN204165443U - The heat exchanger of cooling hydrogen cyanide crude product and the reaction unit of production hydrogen cyanide - Google Patents
The heat exchanger of cooling hydrogen cyanide crude product and the reaction unit of production hydrogen cyanide Download PDFInfo
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- CN204165443U CN204165443U CN201320822077.8U CN201320822077U CN204165443U CN 204165443 U CN204165443 U CN 204165443U CN 201320822077 U CN201320822077 U CN 201320822077U CN 204165443 U CN204165443 U CN 204165443U
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- pipe
- sleeve pipe
- hydrogen cyanide
- aluminium oxide
- porcelain bushing
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- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000012043 crude product Substances 0.000 title claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 238000001816 cooling Methods 0.000 title abstract description 15
- 238000004519 manufacturing process Methods 0.000 title description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 181
- 229910052573 porcelain Inorganic materials 0.000 claims abstract description 58
- 239000000919 ceramic Substances 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 18
- 239000000835 fiber Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 56
- 239000001301 oxygen Substances 0.000 description 56
- 229910052760 oxygen Inorganic materials 0.000 description 56
- 239000007789 gas Substances 0.000 description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 42
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 41
- 238000000034 method Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 35
- 239000002918 waste heat Substances 0.000 description 34
- 239000000463 material Substances 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 229910021529 ammonia Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 229910052710 silicon Inorganic materials 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000000377 silicon dioxide Substances 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 238000005669 hydrocyanation reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- CFEYBLWMNFZOPB-UHFFFAOYSA-N pent-4-enenitrile Chemical compound C=CCCC#N CFEYBLWMNFZOPB-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910000975 Carbon steel Inorganic materials 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PDNNQADNLPRFPG-UHFFFAOYSA-N N.[O] Chemical compound N.[O] PDNNQADNLPRFPG-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- -1 sulphur compound Chemical class 0.000 description 2
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004590 computer program Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The utility model relates to a kind of heat exchanger for cooling hydrogen cyanide crude product, it comprises some pipes, every root pipe in wherein said some pipes includes: the porcelain bushing of the entrance of pipe described in the aluminium oxide containing at least 90wt% and extend through, and each described sleeve pipe includes the separation layer at least partially around described sleeve pipe; And the one or more pads containing at least aluminium oxide of 90wt%, wherein, at least one in described one or more ceramic gasket is round described sleeve pipe above the entrance of described pipe, and described porcelain bushing and described pipe separate.The utility model relates to the reaction unit comprising described heat exchanger further.
Description
the cross reference of related application
This application claims the priority of U. S. application 61/738,795 enjoying in and submit on December 18th, 2012, the full content of this application and disclose incorporated herein.
Technical field
The utility model relates to a kind of reaction unit producing hydrogen cyanide, and described reaction unit comprises the heat exchanger containing some pipes.
Background technology
Traditionally, hydrogen cyanide (" HCN ") carries out plant-scale production according to Andrussow method or BMA method.(for example, see Ullman ' s Encyclopedia of Industrial Chemistry, Volume A8, Weinheim 1987:161-163).Such as, in Andrussow method, under suitable catalyst exists, ammonia can be made in the reactor at high temperature to react with the gas and oxygenous gas that contain methane prepare HCN commercially (see US Patent No. 1,934, No. 838 and US6,596,251).The higher homologue of sulphur compound and methane may affect the parameter of the oxidative ammonolysis reaction of methane.For example, see Trusov, Effect of Sulfur Compounds and Higher Homologues of Methane on Hydrogen Cyanide Production by the Andrussow Method, Russian J.Applied Chemistry, 74:10 (2001): 1693-1697.Contact with ammonium phosphate solution in ammonia gas absorption device by making reactor eluting gas and unreacted ammonia is separated with HCN.By the ammonia gas purification separated, concentrate, for recycling the conversion of HCN.Usually by be adsorbed in water thus to reclaim HCN from the air-flow that the reactor after process flows out.After the HCN reclaimed can be passed through and further refines operation process, to prepare the HCN of purifying.Clean Development Mechanism Project Design Document Form (CDM PDD, Version 3), 2006 (Clean Development Mechanism Project design book, the third edition, 2006) graphically explain the Andrussow production technology of HCN.The HCN of purifying can be used in hydrocyanation, and as the hydrocyanation of olefine-containing group or the hydrocyanation of 1,3-butadiene and allyl acetonitrile, wherein the hydrocyanation of 1,3-butadiene and allyl acetonitrile can be used as producing adiponitrile (" ADN ").In BMA technique, under the condition of actual no oxygen, under platinum catalyst exists, HCN is synthesized with methane and ammonia, consequently create HCN, hydrogen, nitrogen, remaining ammonia and remaining methane (see Ullman ' s Encyclopedia of Industrial Chemistry, Volume A8, Weinheim 1987:161-163).Business operator requires to carry out process safety management to control the danger of hydrogen cyanide (see people such as Maxwell, Assuring process safety in the transfer of hydrogen cyanide manufacturing technology, JHazMat 142 (2007): 677-684).In addition, the discharge from production equipment in HCN manufacturing process observes regulation possibly, and this will affect the economy of HCN production.(see Crump, Economic Impact Analysis For The Proposed Cyanide Manufacturing NESHAP, EPA, May 2000).
When HCN outflow reactor, enter Disengagement zone at it and must cool before reclaiming ammonia and hydrogen cyanide.Wherein a kind of method of cooling reactor product comprises use heat exchanger.US6960333 teaches the indirect plate-tube type heat exchanger of a kind of prolongation for chemical reactor, and especially those are exposed to the method in the service life of the heat exchanger in reduction, nitrogenize and/or carburizing environment.US6960333 further teach silica, aluminium oxide and zirconic porcelain bushing can not provide enough protection for chemistry and physical agent under severe rugged environment, wherein also includes the situation in hydrogen cyanide reactor.US6960333 teaches under these circumstances, and normally used sleeve pipe (comprising known porcelain bushing) is protectiveness, means that it can be degraded, and must monitor it and regularly replace.US6960333 teaches the service life of heat-exchange tube using the sleeve pipe containing nickel-chromium alloy or silicon nitride greatly can increase heat-exchange tube, especially use in hydrogen cyanide is produced.
The heat-exchange tube containing sleeve pipe is used to suffer from many problems with the existing sleeve pipe and technique of producing hydrogen cyanide; hinder its commercial viability; these problems comprise: the protective cannula of cover tube lifetime deficiency; sleeve pipe that may be excessively expensive, and use the sleeve pipe containing the problems referred to above to produce the process efficiency of HCN and the reduction of productivity ratio.
Aluminium oxide ceramics is a kind of with α-Al
2o
3for the ceramic material of principal crystalline phase, wherein Al
2o
3content between 75%-99.9%, usually with batching in Al
2o
3content is classified.According to Al
2o
3mass percentage different, 75 porcelain, 90 porcelain, 95 porcelain, 96 porcelain and 99 porcelain can be divided into, their Al
2o
3% is respectively: 75%, 90%, 95%, 96%, 99% (Liu Weiliang, special cermacis technology, ISBN978-7-5493-0049-5, in August, 2010, p8-20).
Utility model content
The utility model relates to a kind of heat exchanger cooling hydrogen cyanide crude product, it comprises some pipes, every root pipe in wherein said some pipes includes: the porcelain bushing of the entrance of pipe described in the aluminium oxide containing at least 90wt% and extend through, and each described sleeve pipe includes the separation layer at least partially around described sleeve pipe; And the one or more pads containing at least aluminium oxide of 90wt%, wherein, at least one in described one or more ceramic gasket is round described sleeve pipe above the entrance of described pipe, and described porcelain bushing and described pipe separate.
In a specific embodiment, described porcelain bushing comprises the aluminium oxide of at least 94wt%.In another embodiment, described porcelain bushing comprises the aluminium oxide of 90-98wt%.
In another specific embodiment, described one or more ceramic gasket comprises the aluminium oxide of at least 94wt%.In some instances, described one or more ceramic gasket comprises the aluminium oxide of 90-98wt%.
In a specific embodiment, described porcelain bushing extends to the upper surface higher than tube sheet, and the top of every root pipe is connected on the lower surface of tube sheet.
In another specific embodiment, around the described porcelain bushing higher than tube sheet upper surface at least partially, the upper surface of described pad and tube sheet is adjacent for described one or more gasket ring.
The utility model also relates to a kind of reaction unit producing hydrogen cyanide, comprise: reactor and the heat exchanger comprising some pipes, every root pipe in wherein said some pipes includes: the porcelain bushing of the entrance of pipe described in the aluminium oxide containing at least 90wt% and extend through, and each described sleeve pipe includes the separation layer at least partially around described sleeve pipe; And the one or more pads containing at least aluminium oxide of 90wt%, wherein, at least one in described one or more ceramic gasket is round described sleeve pipe above the entrance of described pipe, and described porcelain bushing and described pipe separate.
In a specific embodiment, described one or more ceramic gasket is ceramic fibre pad.
In another specific embodiment, described separation layer is around whole porcelain bushing.In an instantiation, described porcelain bushing can comprise the aluminium oxide of 90-98wt%.In another example, the nonnitrogenous SiClx of described sleeve pipe and nickel-chromium alloy.
In another specific embodiment, described one or more pad contains the aluminium oxide of at least 94wt%.In certain embodiments, described one or more pad contains the aluminium oxide of 90-98wt%.
In a first embodiment, the utility model relates to the consersion unit comprised for the production of hydrogen cyanide, it heat exchanger comprising reactor and comprise some pipes, every root pipe in wherein said some pipes includes: the porcelain bushing of the entrance of pipe described in the aluminium oxide containing at least 90wt% and extend through, and each described sleeve pipe includes the separation layer at least partially around described sleeve pipe; And the one or more pads containing at least aluminium oxide of 90wt%, wherein, at least one in described one or more ceramic gasket is round described sleeve pipe above the entrance of described pipe, and described porcelain bushing and described pipe separate.Described one or more ceramic gasket comprises the aluminium oxide of 94wt%.Described sleeve pipe can have taper shape, taper or flaring intake section.Described sleeve pipe can be free of silicon nitride and nickel-chromium alloy.Described one or more pad can contain the aluminium oxide of 90 ~ 98wt%.Described sleeve pipe has the life-span of at least six months when being exposed to hydrogen cyanide.
In a second embodiment, the utility model relates to the consersion unit comprised for the production of hydrogen cyanide, it heat exchanger comprising reactor and comprise some pipes, every root pipe in wherein said some pipes includes: the porcelain bushing of the entrance of pipe described in the aluminium oxide containing at least 90wt% and extend through, and each described sleeve pipe includes the separation layer at least partially around described sleeve pipe; And contain one or more pads of at least aluminium oxide of 90wt%, wherein, at least one in described one or more ceramic gasket above the entrance of described pipe round described sleeve pipe, and described porcelain bushing and described pipe separate, further, the nonnitrogenous SiClx of wherein said porcelain bushing and nickel-chromium alloy.Described porcelain bushing can contain the aluminium oxide of at least 94wt%.Described one or more ceramic gasket can containing the pottery be selected from by aluminium oxide, silica, zirconia and its group be bonded.Described one or more ceramic gasket can comprise the aluminium oxide of at least 94wt%.
In the third embodiment, the utility model relates to a kind of heat exchanger for cooling hydrogen cyanide crude product, it comprises some pipes, and the every root pipe in wherein said some pipes includes: the sleeve pipe containing at least aluminium oxide of 90wt%, and described sleeve ring is wound with separation layer; And contain one or more pads of at least aluminium oxide of 90wt%, wherein, and described porcelain bushing and described pipe separate.Described sleeve pipe has the life-span of at least six months when being exposed to hydrogen cyanide.Described porcelain bushing and one or more pad all can contain the aluminium oxide of at least 94wt%.Described porcelain bushing extends to the upper surface higher than tube sheet, and the top of every root pipe is connected on the lower surface of tube sheet.Described one or more gasket ring around in described porcelain bushing higher than tube sheet upper surface at least partially, the upper surface of described pad and tube sheet is adjacent.
In the fourth embodiment, the utility model relates to a kind of heat exchanger for cooling chemical reaction product, it comprises some pipes, and the every root pipe in wherein said some pipes includes: the sleeve pipe containing at least aluminium oxide of 90wt%, and described sleeve ring is wound with separation layer; And contain one or more pads of at least aluminium oxide of 90wt%, wherein, wherein said ceramic jacket tube and tube separates, and described sleeve pipe can tolerate fracture and degrade at least six months when being exposed to chemical reaction product.Described chemical reaction product comprises hydrogen cyanide.Described one or more pad can contain the aluminium oxide of at least 90-98wt%.
Accompanying drawing explanation
The rough schematic view of the partial cross sectional of the heat exchanger of Fig. 1 described in an embodiment of the present utility model and reaction system;
Fig. 2 is the reduced graph according to the heat exchanger tube of the utility model embodiment and the sleeve pipe of part separation layer parcel;
Fig. 3 is according to the heat-exchange tube of the utility model embodiment and the reduced graph of sleeve pipe that wraps up completely with separation layer;
Fig. 4 and Fig. 5 shows heat-exchange tube according to two other embodiment of the present utility model and sleeve pipe.
Detailed description of the invention
Term used in the application only for the object describing particular, is not intended to limit the utility model.Unless clearly shown other situation in context, singulative as used herein " " and " being somebody's turn to do " also comprise plural form.It should also be understood that, the term used in this manual " comprise " and/or " including " time describe feature described in existence, entirety, step, operation, parts and/or composition, but do not hinder other features one or more, entirety, step, operation, parts group, the existence of composition and/or their combination or interpolation.
Such as " comprise ", " comprising ", " having ", the term of " containing " or " relating to " and variant thereof should understand widely, and comprise listed main body and equivalent, also have unlisted other main body.In addition, when " being comprised " by transitional phrases, " comprising " or " containing " when drawing component, element set, technique or method step or any other statement, be to be understood that and also contemplate identical component, element set, technique or method step herein, or there is other statement any of transitional phrases before the record of this component, element set, technique or method step or other statement any " substantially by ... composition ", " by ... composition " or " being selected from by ... the group of formation ".
If applicable words, the corresponding structure in claim, material, action and the device of all functions or the equivalent of step comprise for coming any structure of n-back test, material or action in combination with the miscellaneous part of specifically stating in claim.Description of the present utility model for introduce and describe object and provide, but be not exhaustive or the utility model is restricted to disclosed form.Under the prerequisite not departing from scope and spirit of the present utility model, many changes and variant are apparent for the person of ordinary skill of the art.Here select and describe some embodiments, object carries out best explanation to principle of the present utility model and practical application, and make other those of ordinary skill of this area can understand different embodiments of the present utility model and there is multiple change, as being suitable for this special-purpose.Correspondingly, although the utility model is described according to embodiment, but those skilled in the art will recognize that, the utility model can change ground to some extent and implement within the spirit and scope of claims.
Now with detailed reference to specific disclosed theme.Although the claim cited by combination describes by disclosed theme, but is appreciated that disclosed theme is not restricted in these claims by they.On the contrary, disclosed theme covers all replacement schemes, change and equivalent, and these can be contained within the scope of disclosed theme defined by the claims.
Traditionally, hydrogen cyanide (" HCN ") carries out plant-scale production according to Andrussow method or BMA method.In Andrussow method, in the presence of a catalyst, raw material containing methane, ammonia and oxygen carries out reacting to produce hydrogen cyanide crude product at higher than the temperature of 1000 DEG C, and it comprises HCN, hydrogen, carbon monoxide, carbon dioxide, nitrogen, remaining ammonia, remaining methane and water.In some preferred embodiments, containing methane, combined before it reacts generation hydrogen cyanide crude product under the effect of catalyst containing ammonia and oxygenous raw material, form ternary gas mixture.Before flowing through heat exchanger, the temperature of hydrogen cyanide crude product, more than 1000 DEG C, must cool before further, processing.
In Andrussow method technique, the formation of HCN is expressed with following total chemical reaction usually:
2CH
4+2NH
3+3O
2→2HCN+6H
2O
But should be appreciated that, above-mentioned chemical reaction represents the simplification of more complicated kinetic sequence, and wherein part hydrocarbon is first oxidized, thus produces enough heat energy to support from remaining hydrocarbon and ammonia to synthesize the endothermic reaction of HCN.
In the process of synthesis HCN, have following three basic side reactions to occur:
CH
4+H
2O→CO+3H
2
2CH
4+3O
2→2CO+4H
2O
4NH
3+3O
2→2N
2+6H
2O
Except the nitrogen amount that side reaction produces, other the nitrogen be present in crude product depends on the source of oxygen.Although prior art has provided the instruction that oxygen-enriched air or pure oxygen can be used as oxygen sources, do not disclose the advantage using oxygen-enriched air or pure oxygen completely.When using air as oxygen sources, hydrogen cyanide crude product comprises the composition in air, as the nitrogen of 78vol%, and the nitrogen produced in the side reaction of ammonia and oxygen.
The term " air " used in the application refers to the admixture of gas that composition is roughly the same with the original gas composition taking from air (usually at ground level).In some instances, air takes from the air of room temperature environment.Air has following composition, comprises the argon gas of the oxygen of the nitrogen of about 78v%, about 21v%, about 1v% and the carbon dioxide of about 0.04v%, and other a small amount of gas.
Term used in this application " oxygen-enriched air " refers to that composition comprises the admixture of gas higher than content of oxygen in air.Oxygen-enriched air has following composition, comprises the oxygen being greater than 21v%, the nitrogen being less than 78v%, is less than the argon gas of 1v% and is less than the carbon dioxide of 0.04v%.In some embodiments, oxygen-enriched air comprises the oxygen of at least 28v%, the oxygen of such as at least 80v%, the oxygen of such as at least 95v%, or the oxygen of at least 99v%.
Due to a large amount of nitrogen in air, use oxygen-enriched air to compare in the technique of synthesis HCN to have superiority, this is because when using air to produce HCN as oxygen sources, the existence of a large amount of inert gas (nitrogen) will cause synthetic reaction needs in synthesis step, use relatively large device, and the concentration of HCN in product gas can be caused lower.In addition, due to the existence of inert nitrogen, need the more methane of burning to improve the temperature of ternary gas mixture component, make it maintain the temperature of synthesis needed for HCN.This hydrogen cyanide crude product contains HCN, also containing byproduct hydrogen gas, methyl hydride combustion accessory substance (carbon monoxide, carbon dioxide, water), remaining methane and remaining ammonia.But when using air (i.e. 21vol% oxygen), after HCN and callable ammonia being separated with other gas components, the existence of inert nitrogen can make the calorific value of the air-flow of remnants lower than the calorific value needed for energy regenerating.
Therefore, adopt oxygen-enriched air or pure oxygen to replace air-making to have many advantages for HCN, include the ability of recover hydrogen.Other advantages comprise the size improving conversion ratio that conversion of natural gas is HCN and corresponding process units and reduce.Therefore, adopt oxygen-enriched air or pure oxygen, the size of reactor can be reduced by reducing the inert compound entering synthesis technique and reduce at least one parts of gas downstream treating apparatus.Employing oxygen-enriched air or pure oxygen can also reduce the energy this being heated to containing oxygen unstrpped gas consume needed for reaction temperature.In ternary gas mixture, the mol ratio of ammonia and oxygen is 1.2-1.6, as 1.3-1.5; The mol ratio of ammonia and methane is 1-1.5, such as 1.10-1.45; The mol ratio of methane and oxygen is 1-1.25, as 1.05-1.15.Such as, in ternary gas mixture, the mol ratio of ammonia-oxygen is 1.3, and the mol ratio of methane and oxygen is 1.2.In another specific embodiment, in ternary gas mixture, the mol ratio of ammonia-oxygen is 1.5, and the mol ratio of methane and oxygen is 1.15.Oxygen content in ternary gas mixture depends on above-mentioned mol ratio.In certain embodiments, this ternary gas mixture comprises the oxygen of 25-32vol%, the oxygen of such as 26-30vol%.Concrete hydrogen cyanide crude product composition is as shown in table 1.
Table 1 hydrogen cyanide crude product forms
As shown in table 1, utilize air technique to prepare HCN and only produce 13.3v% hydrogen, and oxygen technique can cause hydrogen to be increased to 34.5v%.The amount of hydrogen depends on the concentration of oxygen and the mol ratio of reactant in feeding gas, and changes in the scope of 34-36v% hydrogen.Be not subject to theoretical constraint, can think that the increase of amounts of hydrogen improves the sensitiveness of described sleeve pipe degraded, just as further described herein.
Except table 1, the oxygen content in hydrogen cyanide crude product is low, and preferably lower than 0.5v%, oxygen content high in hydrogen cyanide crude product can cause to be shut down or need to clean.According to the mol ratio of ammonia used, oxygen and methane, the composition alterable of the hydrogen cyanide crude product adopting oxygen Andrussow technique to be formed, as shown in table 2.
Table 2
For preventing the degraded of HCN and unreacted ammonia, the hydrogen cyanide crude product leaving reactor must fast quench, such as, to lower than 300 DEG C, as lower than 250 DEG C or lower.Described hydrogen cyanide crude product can adopt heat exchanger to carry out quenching, and as waste heat boiler, described heat exchanger can contain some pipes, and described Guan Jun is connected on tube sheet.The pipe of described heat exchanger and the construction materials of tube sheet should be selected from decomposition to HCN, have more SA material as HCN hydrolysis.Carbon steel is found to be the preferred material of the low cost of described pipe and tube sheet.The cooled hydrogen cyanide crude product flowed out from waste heat boiler can pass through gas cooler, Ammonia recovery section and HCN refining stage successively.The inlet temperature entering the boiler feedwater of waste heat boiler should be enough high, to prevent the polycondensation of cooled hydrogen cyanide crude product.
Described waste heat boiler, while cooling hydrogen cyanide crude product, is recovered in ternary gas mixture and changes into reaction (the namely burning) heat produced in HCN process.The heat energy that waste heat boiler reclaims is enough in and produces steam under pressure and/or preheating ternary gas mixture.In a detailed description of the invention, waste heat boiler is the heat exchanger of the Natural Circulation for generation of steam, and several places in the circumference near waste heat boiler topmost shift out 2 phase water/vapour mixtures, make it enter drum by steam riser.In drum, steam is separated, and remaining condensate is back to waste heat boiler.When the heat reclaimed is used for preheating ternary gas mixture, the amount of the gas feed stream consumed in synthesis in reactor can be reduced, and significantly can increase the output of the HCN based on every part of gas feed flowmeter.
Described waste heat boiler can be the shell and tube exchanger comprising some pipes, and described some pipes surround by boiler feed water, as boiled water.The temperature of the water around pipe lower than the temperature of hydrogen cyanide crude product, and for making the temperature of pipe lower than the temperature of hydrogen cyanide crude product, as lower than 315 DEG C, or lower than 250 DEG C.Due to the severe rugged environment of hydrocyanation reaction device and hydrogen cyanide crude product, waste heat boiler boiler tube easily ruptures, and needs to increase to safeguard and change, thus causes reducing process efficiency.When the oxygen in ternary gas mixture increases, the fracture of waste heat boiler boiler tube can increase, and also can cause the increase of density of hydrogen in hydrogen cyanide crude product.A kind of scheme makes it not contact with hydrogen cyanide crude product the isolation at least partially of waste heat boiler boiler tube.Preferably, the top of pipe is isolated the high temperature that makes pipe from ternary gas mixture.Although pipe is surrounded by boiler feedwater, the top of tube sheet and pipe fully cannot cool with boiler feedwater.Every root Guan Douke comprises sleeve pipe, to isolate waste heat boiler boiler tube.Sleeve pipe useful ceramics material manufactures.But even if there is sleeve pipe, when it contacts with waste heat boiler boiler tube or waste heat boiler tube sheet, due to the severe rugged environment of high temperature and hydrogen cyanide crude product, it still can rupture.Sleeve pipe of the prior art mainly comprises silicon and/or its oxide, and it can with the hydrogen reaction in hydrogen cyanide crude product.Such as, sleeve pipe of the prior art can containing higher than the silicon of 40wt% and/or its oxide.Therefore, when the oxygen content in ternary gas mixture increases, the increase of the hydrogen in hydrogen cyanide crude product can cause the reduction of overlapping tube lifetime.
Unexpectedly, find when sleeve pipe to be made up of high alumina ceramic and by one or more ceramic gasket, as high alumina ceramic pad around time, the life-span of sleeve pipe can extend.Disrance sleeve also advantageously can extend its life-span and prevent it from rupturing.Configuration pad to be separated with waste heat boiler tube sheet by sleeve pipe, and is separated with waste heat boiler boiler tube.Described pad, also for locating sleeve, is located at the position that can separate with tube sheet and pipe.Be not bound by theory, can think that the space state separated due to sleeve pipe and waste heat boiler boiler tube and pipe reduces thermal stress, thus extend the life-span.This space state can reduce the degraded of salic sleeve pipe and/or gasket material.
Sleeve pipe can be made up of pottery, and pottery can aluminium oxide containing at least 90wt%, as the aluminium oxide of at least 94wt% and the aluminium oxide of at least 98wt%.In scope, described sleeve pipe can comprise the aluminium oxide of 90-98wt%, as the aluminium oxide of 92-98% or the aluminium oxide of 93-95wt%.Sleeve pipe additionally can contain silicon and/or its oxide, zirconium dioxide and combination thereof.But the amount of preferred silicon and/or its oxide is low.On the one hand, in sleeve pipe, the amount of silicon and oxide can lower than 10wt%, as lower than 8wt% or lower than 6wt%.In sleeve pipe, the weight ratio of aluminium oxide and silica can be 9:1-200:1, as 15:1-100:1.An exemplary sleeve pipe can comprise the aluminium oxide of 94wt% and the silica of 6wt%.On the one hand, porcelain bushing can be made up of the pottery of monolithic.Be not bound by theory, can think and use the pottery of monolithic and do not have weld seam to be conducive to the fracture avoiding being caused by thermal expansion.
Described one or more pad also can be pottery, can have similar composition to sleeve pipe.On the one hand, described one or more pad contains the aluminium oxide of at least 90wt%, as the aluminium oxide of at least 94wt% and the aluminium oxide of at least 98wt%.In scope, described pad can comprise the aluminium oxide of 90-98wt%, as the aluminium oxide of 92-98% or the aluminium oxide of 93-95wt%.Ceramic gasket also can contain silicon and/or its oxide, zirconium dioxide and combination thereof.On the one hand, in pad, the amount of silicon and/or its oxide can lower than 10wt%, as lower than 8wt% or lower than 6wt%.An exemplary pad can comprise the aluminium oxide of 94wt% and the silica of 6wt%.Described pad can be ceramic fibre pad.Be not bound by theory, can think that use ceramic fibre pad can reduce the fragility of pad because it has sufficient elasticity.This fiber allows pad slightly movement in reactor operation.
Fig. 1 shows reaction unit 101.Described reaction unit comprises and heat exchanger, the reaction zone that coordinates as waste heat boiler 114.Ternary gas mixture is admitted to reactor by pipeline 102, contacts and react to generate hydrogen cyanide crude product with catalyst bed 103.Ternary gas mixture is by obtaining methane-containing gas, ammonia-containing gas and purity oxygen or oxygen-enriched air mixing.Then hydrogen cyanide crude product stream is through the waste heat boiler 114 containing some pipes 106, and wherein hydrogen cyanide crude product flows through some pipes, to cool hydrogen cyanide crude product and generating steam in the shell side of waste heat boiler 114.The number of pipe 106 can become with the size of reactor.The shell side of waste heat boiler is separated by tube sheet 110 and reactor, and the welded top of pipe 106 is on tube sheet 110.Tube sheet 110 can be the taper shape shown in plate or Fig. 1.The part being directly in the reactor on tube sheet 110 is cast ceramic material 111, and it contains several holes matched with the pipe 106 of waste water boiler.Hole on cast material 111 is connected with the pipe 106 in waste heat boiler 114 by using porcelain bushing 105, and its middle sleeve 105 can put into pipe 106.In addition, porcelain bushing 105 is connected in the outlet 104 of reactor by hole.As shown in figures 1-5, every root pipe 106 all comprises porcelain bushing 105.Pipe 106 is surrounded by boiler feedwater 113.The lower surface of tube sheet 110 also can contact with boiler feedwater 113.When hydrogen cyanide crude product stream is through waste heat boiler 114, it is cooled to temperature lower than 300 DEG C, as lower than 275 DEG C or lower than 250 DEG C, then leaves reactor by pipeline 107, and can be further processed.
Before by sleeve pipe 105 Inserting Tube 106, pad 108 is placed on tube sheet 110.As shown in Figures 2 and 3, in one embodiment, sleeve pipe 105 can be isolated by the thrust 115 on sleeve pipe 105, makes it directly not contact with pipe 106 with tube sheet 110.Thrust 115 can be configured to prevent sleeve pipe 105 from slipping over pad 108.Although illustrate only a thrust, multiple thrust can be used without restriction.Be not bound by theory, even if can think that sleeve pipe 105 there occurs certain degraded, but by making sleeve pipe 105 comprise service life that thrust 115 can extend sleeve pipe.In other embodiments, as shown in Figures 4 and 5, the sleeve pipe 105 not having thrust 115 can also be used.Once by sleeve pipe 105 Inserting Tube 106, then the lubrication pin with tapering point can be inserted into the top of sleeve pipe.Described pin and can be enough to hinder the other materials forming the flowing of the ceramic cement of casting material 111 to form by timber, polytetrafluoroethylene (PTFE).For simplicity, in Fig. 2-5, all show the position of cast material 111, but should be understood to casting material 111 and completely covers tube sheet 110, and round the every root sleeve pipe 105 shown in Fig. 1.Once after pin puts in place, ceramic cement is poured on tube sheet 110 with the bottom of forming reactions device.After cement solidification, pin is taken out from ceramic casting material, to form the hole of supplied gas circulation.Described pin can re-lubrication and reinserting.Multilayer cast material can be cast in the same way.In one embodiment, the cast material for the second layer of casting can be made up of the material being different from ground floor, as material that is more wear-resisting and more mechanical resistant stress.When after cement solidification, again pin is removed.Then catalyst support is placed in the top of casting material, third time injects cast material to form sealing between catalyst support and reactor wall.Then catalyst 103 is placed in catalyst support.For simplicity, the situation of the inside reactor on catalyst is not shown in Fig. 1.
Pipe 106 is connected to cast ceramic material 111 by porcelain bushing 105.Porcelain bushing 105 is separated by pad 108 and tube sheet 110, contacts with tube sheet 110 to prevent porcelain bushing 105 with pipe 106.Pad 108 is engaged in porcelain bushing 105 around securely, enters in pipe 106 to prevent porcelain bushing 105.Pad 108 is around porcelain bushing 105 above tube sheet 110, and its external diameter is greater than the diameter of pipe 106.The upper surface of the tube sheet 110 that pad 108 and pipe 106 are welded thereon is adjacent.In certain aspects, pad 108 does not have gluing or is otherwise attached on tube sheet 110.In these areas, the cast of cast material 111 can maintain the position of pad 108.Although only show a pad in Fig. 2-5, also multiple pad can be used.
Porcelain bushing 105 be shorter in length than pipe 106.The length of every root pipe 106 can be several meters, and the length of porcelain bushing can be shorter than 20cm.Porcelain bushing 105 extends to higher than tube sheet 110 at least 1cm, as at least 3cm or at least 5cm.In addition, porcelain bushing 105 may extend to lower than tube sheet 110 at least 5cm, as at least 8cm or at least 10cm.Preferred most of sleeve pipe 105 is positioned at pipe 106.In one embodiment, the length of described sleeve pipe 105 enough extends under the water surface of boiler feedwater 113.For simplicity, show the position of boiler feedwater 113 in figs. 2-5, but should be appreciated that boiler feedwater 113 can contact with tube sheet 110 around the pipe 106 shown in Fig. 1.
Porcelain bushing 105 can be wound with isolated material 109 at least partially, as suitable inorganic insulation paper.The 3M that exemplary inorganic insulation Zhi Shi 3M company sells
tMceQUIN and 3M
tMtherma Volt.As shown in Figure 2, isolated material 109 can be positioned at pipe 106 at least partially around sleeve pipe 105.In another embodiment, as shown in Figure 3, isolated material 109 can around the whole length of sleeve pipe 105.The thickness of isolated material 109 is preferably uniform, and namely change is no more than 0.5cm, and can change in the scope of 0.05-0.2cm.Described isolated material can further compress before use.In one embodiment, as shown in Figure 2, pipe 106 and sleeve pipe 105 separate by isolated material 109, and it contacts with the inner surface of pipe 106.Preferably between isolated material 109 and pipe 106, there is no space, therefore formed between sleeve pipe 105 and pipe 106 and be sealed and matched.The inner surface of sleeve pipe 105 with pipe 106 separates by isolated material 109.This can prevent the further degraded of sleeve pipe 105.
As seen in figs. 2-5, porcelain bushing 105 can containing parallel inwall.The thickness of sleeve pipe can change in the length of sleeve pipe.Such as, the tube wall being positioned at the sleeve pipe 105 on pad 108 can than the thickness of pipe wall be positioned under pad 108.Be not bound by theory, can think that the thick casing wall on pad increases the intensity of sleeve pipe, and the thin-walled be positioned under pad 108 causes internal diameter to increase, thus the capacity resulting through sleeve pipe increase.Thick upper wall also can prevent sleeve pipe 105 from entering pipe 106.In other respects, porcelain bushing 105 can be configured to the cylindrical tube as having taper shape, taper or bellmouth entrance part (not shown), the pipe of described shape can be put in the entrance 112 of some waste heat boiler boiler tubes 106 described in every root, thus by one or several pads 108, porcelain bushing 105 is spaced apart with the inner surface of pipe 106.Described taper shape, taper or bellmouth entrance part also can prevent sleeve pipe 105 from entering pipe 106.Such as, the diameter of conical, taper or bellmouth entrance part can be greater than the diameter of entrance 112.Pad 108 of the present utility model is configured to coordinate securely and be looped around around described sleeve pipe, and can be the flat band shape be wound on sleeve pipe.Pad preferably contains the aluminium oxide of at least 90wt%, as the aluminium oxide of 90-98wt%, as the aluminium oxide of 93-95wt%.
As shown in Figure 5, the diameter of entrance 112 is less than the diameter of pipe 106.Tube sheet 110 may extend across tube wall, produces a ledge.At this on the one hand, porcelain bushing 105 is arranged on a position, can extend through entrance 112 and enter pipe 106.The diameter of porcelain bushing is less than entrance 112, is therefore less than the diameter of pipe 106.As shown in Figure 4, pad 108 can extend across tube wall 110, or as shown in Figure 5, flushes with tube sheet 110.On the other hand, as shown in Figure 4, the diameter of entrance 112 is similar to the diameter of pipe 106, and thus tube wall flushes with the edge of tube sheet 110.
The porcelain bushing used as required in the application, time in it is exposed to chemical reaction product (as hydrogen cyanide crude product) under high corrosion condition and/or reducing environment, there is the life-span of at least 1 month, as the life-span of at least 6 months, the life-span of at least 1 year, or the life-span of at least 3 years, wherein said high corrosion condition comprises the Exhaust Gas of needs to heat and cools fast.Such as, in HCN produces, the hot exhaust gas comprising hydrogen cyanide crude product must be quickly cooled to lower than 300 DEG C or lower than 275 DEG C or lower than 250 DEG C, to prevent the decomposition of HCN from 1000-1400 DEG C (as preferred 1000-1200 DEG C).Due to the high temperature of hydrogen cyanide crude product, before first it enter waste heat boiler and then contact with the pipe of lower temperature, sleeve pipe is in harsh environment.
In certain embodiments, sleeve pipe and the pad aluminium oxide all containing at least 90wt%.On the one hand, the aluminium oxide in sleeve pipe and pad can be alpha-aluminium oxide.In sleeve pipe and pad, the amount of preferred aluminium oxide is the function of the amount of oxygen that ternary gas mixture exists.Like that as described herein, when the amount of oxygen increases above the amount naturally existed in air, hydrogen cyanide crude product is just more responsive to sleeve pipe.Especially, the hydrogen in hydrogen cyanide crude product can react with silicon and oxide thereof, causes the material of the silicon containing high-load and/or its oxide to reduce.If existed in sleeve pipe and pad more than the silicon of 10wt% and/or its oxide, then sleeve pipe and pad become protectiveness, and service life reduction.This just needs to change expensive sleeve pipe continually, and needs off-response device.Due to the ternary gas mixture of preferred high oxygen concentration, be therefore necessary the content of silicon in limiting boot and pad and/or its oxide.Therefore, the silicon in sleeve pipe and pad and/or its oxide should lower than 10wt%, as 0.01 ~ 5wt%.Oxygen-enriched air or purity oxygen is used to have advantage as oxygen-containing gas.Therefore, in certain embodiments, porcelain bushing and one or more pad contain silicon lower than 10wt% and/or its oxide, as lower than 7.5wt% or lower than the silicon of 5wt% and/or its oxide.
Various control system can be used to regulate reaction gas flow.Such as, can use traffic meter to measure flow velocity, the temperature and pressure of reacting gas incoming flow, thus allow " in real time " of the control system flow velocity that provides pressure and temperature to compensate to feed back to operator and/or control appliance.Recognize as those of ordinary skill in the art, aforementioned function and/or technique can with system, method or computer program imbodies.Such as, function and/or technique can realize in the mode being recorded in the computer-executable program instructions in computer readable storage devices, when being retrieved by computer processor and performing, the function of computer for controlling system executed embodiment description herein and/or technique.In a particular embodiment, computer system can comprise one or more center processing unit, computer storage (as read-only storage, random access memory) and a data storage device (as a hard drive).Computer executable instructions can use any suitable computer programming language (as C++, JAVA etc.) to programme.Accordingly, this aspect of the present utility model can to adopt the mode of whole software implementation (comprising) or the mode in conjunction with software and hardware aspect embodiment.
Can learn from above-mentioned explanation, clearly the utility model can be well suited for realize target and reach mentioned advantage and disclosure institute inherent advantages here.Although described preferred embodiment of the present utility model for the purpose of this disclosure, but be understandable that, change that is apparent to those skilled in the art and that can complete under spirit of the present utility model can be carried out.
There is provided following examples to set forth this technique.Be understandable that, the object of these embodiments only for setting forth, and any restriction to the utility model scope can not be caused.
Embodiment 1
By forming ternary gas mixture in conjunction with oxygen-enriched air, ammonia-containing gas and methane-containing gas.In this ternary gas mixture, the mol ratio of ammonia and oxygen is 1.3:1, and the mol ratio of methane and oxygen is 1.2.The ternary gas mixture comprising 27-29.5v% oxygen is reacted under the existence of platinum/rhodium catalyst, forms hydrogen cyanide crude product.In course of reaction, produce hydrogen, in hydrogen cyanide crude product, comprise the hydrogen of 34.5v%.Waste heat boiler comprises the tube sheet of carbon steel and the waste heat boiler boiler tube of 392 carbon steels.Every root pipe surrounding is all surrounded by boiling water.Every root pipe includes sleeve pipe, and described sleeve pipe is containing the aluminium oxide of 94wt% and the silica of 6wt%.The length of every root waste heat boiler boiler tube is 914.4cm, and the length of sleeve pipe is 17.8cm.Described sleeve pipe extends through the entrance of pipe, make a part for sleeve pipe extend to higher than waste heat boiler boiler tube entrance 5.01cm and extend into waste heat boiler boiler tube 12.7cm, namely lower than entrance.Sleeve pipe and waste heat boiler boiler tube are separated by separation layer, described separation layer has the uniform thickness of 0.1cm, and it is wrapped up by ceramic fibre compressed paper and forming.The whole length of described separation layer annular sleeve.Comprise the sleeve pipe of ceramic gasket around isolation of 94wt% aluminium oxide and 6wt% silica.The temperature entering the hydrogen cyanide crude product of sleeve pipe is 1150 DEG C, and when leaving waste heat boiler, it is cooled to 230 DEG C.Under continuous operation, the service life of sleeve pipe is 4-5.
Embodiment 2
Except not using pad, use the sleeve pipe identical with embodiment 1 and separation layer, the preparation of hydrogen cyanide crude product and cooling are as shown in Example 1.Sleeve pipe has the life-span of 2 years.
Comparative example A
Except making sleeve pipe except not using separation layer and contacting with heat-exchange tube, the preparation of hydrogen cyanide crude product and cooling are as shown in Example 1.Sleeve pipe has the life-span being less than 6 months, and multiple sleeve pipe has just damaged when reacting and starting.
Comparative example B
Except using the sleeve pipe of silicon nitride composition, the preparation of hydrogen cyanide crude product and cooling are as shown in Example 1.Sleeve pipe has the life-span being less than 6 months, and multiple sleeve pipe has just damaged when reacting and starting.2 week of reactor down-time, with more casing replacing, causes cost to improve and the productive rate reduction of HCN.
Comparative example C
Except sleeve pipe is made up of the aluminium oxide of 50wt% and the silica of 50wt%, the preparation of hydrogen cyanide crude product and cooling are as shown in Example 1.As shown in table 1, when adopting purity oxygen as oxygen-containing gas during non-air, hydrogen cyanide crude product has higher hydrogen content.Hydrogen in hydrogen cyanide crude product and the silica in sleeve pipe react, and sleeve pipe is degraded.The life-span of sleeve pipe, multiple sleeve pipe just damaged when reacting and starting less than 6 months.2 week of reactor down-time, with more casing replacing, causes cost to improve and the productive rate reduction of HCN.
Comparative example D
Except sleeve pipe is made up of nickel-chromium alloy, the preparation of hydrogen cyanide crude product and cooling are as shown in Example 1.Nickel-chromium alloy conducts electricity, and can react with hydrogen cyanide crude product.The life-span of sleeve pipe was less than 3 months, and multiple sleeve pipe has just damaged when reacting and starting.2 week of reactor down-time, with more casing replacing, causes cost to improve and the productive rate reduction of HCN.
Comparative example E
Except pad is made up of nickel-chromium alloy, the preparation of hydrogen cyanide crude product and cooling are as shown in Example 1.Nickel-chromium alloy conducts electricity, and can react with hydrogen cyanide crude product.Pad is degraded, and the life-span of sleeve pipe was less than 6 months.Multiple sleeve pipe has just damaged when reacting and starting.In addition, after crackle or pad degraded appear in pad, if sleeve pipe falls into waste heat boiler boiler tube, then whole reactor all can be damaged.At least 2 week of reactor down-time is with more casing replacing and repair reactor, causes cost to improve and the productive rate reduction of HCN.
Comparative example F
Except pad is made up of the aluminium oxide of 80wt% and the silica of 20wt%, the preparation of hydrogen cyanide crude product and cooling are as shown in Example 1.As shown in table 1, when when employing purity oxygen, non-air is as oxygen-containing gas, hydrogen cyanide crude product has higher hydrogen content.Hydrogen in hydrogen cyanide crude product and the silica in pad react, and pad is degraded.The life-span of sleeve pipe, multiple sleeve pipe just damaged when reacting and starting less than 6 months.At least 2 week of reactor down-time, with more casing replacing, causes cost to improve and the productive rate reduction of HCN.
Claims (6)
1. one kind cools the heat exchanger of hydrogen cyanide crude product, it is characterized in that, described heat exchanger comprises some pipes, every root pipe in wherein said some pipes includes: the porcelain bushing of the entrance of pipe described in the aluminium oxide containing at least 90wt% and extend through, and each described sleeve pipe includes the separation layer at least partially around described sleeve pipe; And the one or more pads containing at least aluminium oxide of 90wt%, wherein, at least one in described one or more ceramic gasket is round described sleeve pipe above the entrance of described pipe, and described porcelain bushing and described pipe separate.
2. heat exchanger according to claim 1, is characterized in that, described porcelain bushing extends to the upper surface higher than tube sheet, and the top of every root pipe is connected on the lower surface of tube sheet.
3. heat exchanger according to claim 2, is characterized in that, around the described porcelain bushing higher than tube sheet upper surface at least partially, the upper surface of described pad and tube sheet is adjacent for described one or more gasket ring.
4. produce the reaction unit of hydrogen cyanide for one kind, it is characterized in that, described reaction unit comprises: reactor and the heat exchanger comprising some pipes, every root pipe in wherein said some pipes includes: the porcelain bushing of the entrance of pipe described in the aluminium oxide containing at least 90wt% and extend through, and each described sleeve pipe includes the separation layer at least partially around described sleeve pipe; And the one or more pads containing at least aluminium oxide of 90wt%, wherein, at least one in described one or more ceramic gasket is round described sleeve pipe above the entrance of described pipe, and described porcelain bushing and described pipe separate.
5. reaction unit according to claim 4, is characterized in that, described one or more ceramic gasket is ceramic fibre pad.
6. reaction unit according to claim 4, is characterized in that, described separation layer is around whole porcelain bushing.
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| US201261738795P | 2012-12-18 | 2012-12-18 | |
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| CN (1) | CN204165443U (en) |
| TW (1) | TWM488497U (en) |
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