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- US8399728B2 - Absorber demethanizer for methanol to olefins process - Google Patents
- US3095274A - Hydrogen liquefaction and conversion systems - Google Patents
- BINDER KB 23 Benchtop Refrigerated Incubator with Compressor Technology (0.7 cu. ft.)
- Updating K-0.4 and AK-1.5 type of medium-pressure air-fractionating installations
- Federal Register of Legislation - Australian Government
- The List of Products with HS Codes Subject to TR CU 010 Certificate and Declaration
US8399728B2 - Absorber demethanizer for methanol to olefins process - Google PatentsVIDEO ON THE TOPIC: Cryogenics Working Principle , Animation Importance and Advantageous
June D. It is known that normal hydrogen is a mixture of two gases referred to as ortho hydrogen and para hydrogen, and that the equilibrium concentration of ortho hydrogen and para hydrogen varies with temperature. At temperatures above about F. It is also known that ortho hydrogen conversion is an exothermic reaction, releasing about B. The percentage of liquid hydrogen that is lost by vaporization is a function of the ortho hydrogen composition of the liquid hydrogen at the time ortho hydrogen conversion begins, such as the time liquid hydrogen is introduced into a storage vessel, and a function of the degree of completeness of conversion of ortho hydrogen to para hydrogen, that is, the storage period.
Thus it is not practicable to store liquefied normal hydrogen. It has been proposed in the past to accelerate conversion of ortho hydrogen to para hydrogen by the use of a catalyst placed in the liquid receiving zone of a hydrogen liquefier in intimate contact with liquefied hydrogen under atmospheric pressure.
With this arrangement, it is possible to produce liquid hydrogen of high para concentration which may be stored at atmospheric pressure without appreciable liquid loss. However, there is no saving in power since the power required to produce a given quantity of liquid hydrogen of high para concentration by catalytic conversion at atmospheric pressure is substantially the same as the power required to produce the same quantity of liquid hydrogen of similar para hydrogen concentration when autogenous ortho hydrogen conversion takes place.
It is therefore an object of the present invention to atent provide a novel method of and apparatus for producing liquid hydrogen of high para concentration. Another object is to provide a novel method of and apparatus for producing liquid hydrogen of a high para concentration in which the power required per mol of product is materially less than the power requirements of prior cycles.
In accordance with the principles of the present invention liquid hydrogen is subjected to catalytic treatment to effect conversion of ortho hydrogen to para hydrogen under novel conditions such that the inherent heat of conversion is utilized to produce a fluid possessing high internal energy and the internal energy of the fluid is used to reduce the power required to produce the liquid hydrogen.
In particular, in the method and apparatus provided by the present invention catalytic conversion of ortho hydrogen to para hydrogen is accomplished in such a manner so that the heat of conversion vaporizes liquefied gas under superatmospheric pressure, the liquefied gas being at a temperature corresponding to the desired para hydrogen concentration and the vaporized liquefied gas being under superatmospheric pressure possesses high internal energy which is utilized to materially reduce hydrogen liquefaction power requirements notwithstanding the relationship of pressure and heat of vaporization.
The feature provided by the present invention of catalytically converting ortho hydrogen to para hydrogen under conditions such that the heat of conversion effects varporization of a liquefied gas under superatmospheric pressure lends to the utilization of a liquefaction cycle of the type employing a recirculated refrigeration fluid under superatmospheric pressure. Refrigeration fluid is compressed, cooled and expanded to a superatmospheric pressure and partially liquefied and hydrogen feed is converted catalytically to efiect vaporization of liquefied refrigeration fluid.
Refrigeration fluid may comprise hydrogen gas or a gas other than hydrogen, and the hydrogen feed and the refrigeration fluid may flow through the cycle as separate streams with the hydrogen feed being under any desired pressure when catalytically treated to accelerate conversion of ortho hydrogen to para hydrogen. Also, hydrogen feed and refrigeration fluid may comprise a common stream of compressed hydrogen gas which is expanded to a superatmospheric pressure and introduced into a catalytic treating zone with the hydrogen feed in liquid phase and the refrigeration fluid partly liquefied, the liquid hydrogen teed being catalytically converted and the heat of conversion vaporizing liquefied refrigeration fluid.
As discussed above, the hydrogen feed may be catalytically converted at any desired pressure, such as atmospheric pressure or a relatively high superatmospheric pressure or at any intermediate pressure including the superatmospheric pressure of the liquefied gas vaporized by the heat of conversion.
In cycles in which the hydrogen feed is under a superatmospheric pressure during the catalytic conversion process, the converted hydrogen may be expanded to a lower pressure, such as atmospheric pressure, and hydrogen vapor flashed during this expansion may be recirculated in the cycle. The hydrogen feed may be catalytically converted while in liquid phase or while under a pressure above the critical pressure of hydrogen.
The foregoing and other objects and features of the present invention will appear more fully from the following detailed description considered in connection with the accompanying drawings which disclose several embodiments of the invention. It is to be expressly understood however that the drawings are designed for purposes of illustration only and not as a definition of the limits of the invention, reference for the latter purpose being had to the appended claims. FIGURE 1 is a diagrammatic showing of a hydrogen liquefaction and conversion cycle constructed in accordance with thepresent invention;.
In FIGURE 1 of the drawings a hydrogen liquefaction and conversion cycle embodying the principles of the present invention is disclosed therein with a stream of normal hydrogen at atmospheric temperature and pressure and free of moisture and other condensibles including oxygen and nitrogen being fed thereto through conduit and merged with a stream of gaseous hydrogen of high para concentration at substantially atmospheric temperature and pressure in conduit 11, the gaseous hydrogen stream of high para concentration being derived from the process in a manner described below.
The merged streams are passed to a first stage compressor 12 by which the pressure is increased to a superatmospheric pressure below the critical pressure of hydrogen which may be referred to as an intermediate pressure.
The hydrogen stream under intermediate pressure is conducted by conduit 13 to the inlet of a second stage compressor 14 together with a stream of gaseous hydrogen under the intermediate pressure passed by conduit 15 connected to the conduit 13, the stream of gaseous hydrogen in the conduit 15 having a para composition greater than normal and being derived from the liquefaction and conversion process as described below.
The stream of hydrogen gas fed to the compressor 14 from the conduits 10, 11 and 15 is compressed to a relatively high pressure as required for partial liquefaction described below and comprises the hydrogen feed as well as a refrigeration fluid of the cycle. The high pressure hydrogen gas is cooled to a relatively low temperature by warming the gaseous hydrogen streams passed by conduits 11 and 15 and extraneous refrigeration may also be employed.
As shown, the high pressure hydrogen gas is conducted by conduit 16 to pass 17 of a multi-pass heat exchange device 18 and from the cold end of the pass 17 through conduit 19 to pass 20 of a multi-stage heat exchange device The heat exchange devices 18 and 21 include passes 22 and 23, respectively, connected in series by conduit 24, and passes 25 and 26, respectively, connected in series by conduit 27, through which relatively cold gaseous hydrogen streams at atmospheric pressure and at the intermediate pressure, respectively, flow in countercurrentheat exchange effecting relation with the high pressure hydrogen gas.
The conduits 11 and 15 are respectively connected to the warm ends of the passes 22 and The heat exchange device 18 may include a shell 30 defining a chamber enclosing the heat exchange passes 17, If desired, the conduit 33 maybe connected to a region of subatmospher'ic pressure' 4 Cooled high pressure hydrogen is withdrawn from the pass 20 at the cold end of the heat exchange device 21 and conducted by a conduit 35 to an expansion valve 36 by which its pressure is reduced to an intermediate superatmospheric pressure, the efliuent of the expansion step being introduced by conduit 37 into a chamber 38 defined by vessel The temperature and pressure conditions existing downstream of the expansion valve 36 are such that a portion of the hydrogen entering the chamber 38 is in liquid phase, the liquefied hydrogen collecting in a pool The catalyst 41 may comprise a mass or bed of small particles of any one of a number of known materials capable of accelerating conversion of ortho hydrogen, such as ferric hydroxide, for example.
Catalytically converted hydrogen in liquid phase is withdrawn from the chamber 38 by way of a conduit 42, conducted through pass 43 of heat exchange device 44 in countercurrent heat exchange efiecting relation with a cold fluid stream described below, expanded in a valve 45 to atmospheric pressure and introduced into a liquid receiving chamber 46 defined by vessel 47 which may comprise a storage vessel.
Converted liquid hydrogen of high para concentration collects in a pool 48 from which it may be withdrawn through conduit 49 provided with a control valve Hydrogen vapor. This heat exchange step reduces the together comprise the refrigeration fluid, are withdrawn from the chamber 38 through the conduit 29 and then flowed through pass 26 of heat exchange device 21 andpass 25 of heat exchange device 18 as described above.
The stream of normal hydrogen is mixed with a stream of hydrogen vapor under atmospheric pressure in conduit 11 and the combined streams are compressed in compressor 12 to an intermediate pressure of p.
Compressed hydrogen from the compressor 12 and refrigeration fluid comprising gaseous hydrogen under the intermediate pressure in conduit 15 are compressed in the compressor 14 to a high pressure of about p. The stream of high pressure hydrogen gas enters the pass 17 of the heat exchange device 18 at about 80 F. The catalytically converted liquid hydrogen is cooled upon flowing through the heat exchange device 44, further cooled to about F. However the exact para hydrogen concentration of the liquid in pool 48 will depend upon the residence time in the chamber Upon expansion of the converted liquid hydrogen from the intermediate pressure of 80 p.
The refrigeration fluid at the intermediate pressure leaves the warm end of the heat exchange device 21 at about F. In order to liquefy the hydrogen feed at the intermediate pressure of 80 p.
Thus, 7. The feed to the compressor 14 comprises 6. It is seen from the foregoing that about 7. As discussed above, conversion of ortho hydrogen to para hydrogen is an exothermic reaction releasing about Btu.
This is manifest by considering the quantity of liquid hydrogen vaporized at atmospheric pressure and at various superatmospheric pressures upon conversion of one pound mol of liquid hydrogen as shown in the following table:. While a saving in power is obtained by catalytically converting ortho hydrogen to para hydrogen at anyintermediate superatmospheric pressure below the critical pressure of hydrogen, it has been determined that substantial power savings may be realized when eifecting the catalytic conversion at intermediate pressures between 60 p.
Although the percentage of converted liquid hydrogen that flashes into vapor upon expansion from the superatmospheric conversion pressure to atmospheric pressure increases as the conversion pressure is raised up to the critical pressure of hydrogen, it has been determined that the power required to produce ,1 mol of liquid para hydrogen decreases as the conversion pressure increases above atmospheric pressure.
A plot of power requirements against superatmospheric conversion pressures does not define a straight line relationship throughout a range of conversion pressures between atmospheric pressure and the critical pressure of hydrogen, but demonstrates that the power required to produce 1 mol of liquid para hydrogen rapidly decreases as the conversion pressure increases from atmospheric pressure to a pressure in the neighborhood of 60 p.
At conversion pressures between 1 30 p. At a conversion pressure of about 60 p. It is believed the possible power saving varies in the foregoing manner due to variations in the percentage of converted liquid flashed upon its expansion from the conversion pressure to atmospheric pressure and also due to changes with pressure of the density of liquid and gaseous hydrogen.
Z The percentage of converted liquid hydrogen flashed as vapor upon expansion from the superatmospheric conversion pressure to atmospheric pressure increases according to a substantially straight line function up to conversion pressures in the neighborhood of about p. Also, the density of hydrogen vapor gradually increases with pressure while the density of hydrogen liquid gradually decreases with pressure, from atmospheric pressure to about p.
Since the difference in density between hydrogen liquid and hydrogen vapor determines the driving force for separating the phases it is believed that at conversion pressures above p. Furthermore, the conversion pressure determines the para equilibrium concentration of the converted liquid hydrogen. At a conversion pressure of about p. At a conversion pressure of 60 p. At conversion pressures of 80 p.
This is satisfactory para concentration for most storage requirements. The liquefaction and conversion cycle shown in FIG URE 2 of the drawings incorporates the novel cfeature provided by the present invention of catalytically converting hydrogen under such conditions as to vaporize by the heat of conversion liquefied gas at superatmospheric pressure as described above, in connection with a cycle employing an expansion engine for obtaining more complete utilization of the internal energy of the liquefied gas vaporized by the heat of conversion.
As shown, a stream of normal hydrogen at atmospheric temperature and pressure and free of moisture and impurities including traces of oxygen and nitrogen is introduced to the cycle through conduit 50 and merged with a recycled stream of hydrogen vapor at atmospheric pressure having a higher than normal para concentration in a conduit 51, the merged streams being fed to a compressor 52 for compression to a high pressure required to meet the lique-, faction requirements. The high pressure hydrogen gas from the compressor is conducted by conduit 53 to pass 54 of a heat exchange device 55 wherein the hydrogen is cooled to a relatively low'temperature.
The liquid refrigerant may be introduced at atmospheric pressure into the'heat exchange device through conduit 59 and the vapor zone 58 may be connected by conduit 60 to a region'of low pressure. From the cold end of the heat exchange pass 54 the cooled high pressure hydrogen is conducted by conduits 61 to pass 62 of heat exchange device 63 wherein the hydrogen is further cooled in heat exchange relation with the cold fluid streams described below. Thereafter the cooled high pressure hydrogen is expanded in valve 64 to a'superatmospheric pressure and introduced in partially liquid phase into a chamber 65 defined by vessel The liquefied hydrogen collects in apool 67 in the chamber 65 and, in accordance with the principles of the present invention, a catalyst 68 is located in the chamber in intimate contact with the liquid hydrogen in the pool 67 to efiect conversion of ortho hydrogen, withvaporization of liquid hydrogen by the heat of conversion, and provide liquid hydrogen of a maximum para concentration determined by the existing temperature.
Converted liquid hydrogen is withdrawn from the chamber through conduit 69, conducted through pass 70 of heat exchange device 71, expanded to atmospheric pressure in valve 72 and introduced into liquid receiving chamber 73 of vessel 74 where it collects as a pool 75 from which it may be withdrawn through conduit 76 provided with a control valve 77'. Vapor flashed upon expansion of convert-ed liquid hydrogen from the superatmospheric conversion pressure to atmospheric pressure, which vapor is of high para concentration, is withdrawn from the chamber 73 through conduit 78 and conducted through pass 79 of heat ex-v change device 71 in countercurrent heat exchange effecting relation with converted liquid hydrogen and then passed in countercurrent heat exchange eflecting relation Withthe high pressure hydrogen gas.
As shown, the hydrogen vapor stream from the warm end of the heat exchangedevice 71 is conducted ,by conduit 80 to pass 81 of the heat exchange device 63, and then introduced by way of conduit 82 to pass 83 of the heat exchange device 55, the warm end of the pass 83 being connected to the conduit The refrigeration fluid comprising the unliquified portion of, the high pressure hydrogen gas and liquid hydrogen vaporized by the heat of conversion is withdrawn from the chamber 65 through conduit 84 and conducted under the superatmospheric conversion pressure to pass 85 of the heat exchange device 63 for countercurrent heat exchange effecting relation with the high pressure hydrogen gas.
The effluent from the expansion engine in conduit 88 may be conducted through conduit 89 and control valve 90 and merged with the hydrogen vapor of high para concentration in conduit 80, or may be conducted through conduit 91 and control valve 92 for merging with the hydrogen vapor of high para concentration in conduit 78 on the cold side of the heat exchange device There is an optimum temperature at which the hydrogen vapor under the conversion pressure is withdrawn from the heat exchange device 63 in order to obtain maximum refrigeration.
Also, the temperature of the expansion engine efliuent will be influenced by operating conditions as understood by those skilled in the art and hence the point of introduction of the effluent to the heat exchange zone may vary for different cycles.
In any event it is desired to introduce the efiiuentin such a manner as to obtain more eflicient heat interchange and thus utilize to the fullest extent refrigeration obtained by the expansion step. Thus, as illustrated, the effluent from the expansion engine may be added to the warmed hydrogen vapor of high para concentration entering the cold end of the heat exchange devices 63 or In addition, in some instances it may be desirable to introduce the expansion engine efliuent to the pass 79 at an intermediate point along the length of the heat exchange device The high pressure hydrogen is cooled to about F.
The cooled high pressure hydrogen is further cooled in the heat exchange device 63 to about 40 F. Liquid forming the pool 67 is in intimate contact with the catalyst 68 to accelerate conversion of ortho hydrogen and establish an equilibrium concentration corresponding to -4l0 F.
The converted liquid is passed by conduit 69 through heat exchange device 71 and expanded in valve 71 to atmospheric pressure and introduced into the liquid receiving chamber 73 at about F. Upon expansion of converted liquid hydrogen from 80 pounds p. With the hydrogen gas at a pressure of p. Consequently the refrigeration fluid comprises about 5.
The refrigeration medium is warmed in pass 35 to about F. The efliuent may be passed through valve 90 and added to the low pressure hydrogen vapor entering the coldend of the heat exchange pass Thus, the stream of hydrogen vapor leaving the warm end of the heat exchange pass 83 and flowing to the conduit 51 comprises about 6 mols and about 1 mol of normal hydrogen is introduced to the cycle through conduit This results since additional refrigeration is obtained upon operation of the expansion engine The latter operation is made possible by the feature of the present invention of catalytically converting the hydrogen feed under such conditions so that the heat of conversion vaporizes liquefied gas under superatmospheric pressure, the pressure of the vaporized liquefied gas falling within a pressure range adequate for subsequent work expansion to atmospheric pressure.
While the refrigeration obtained by expanding the refrigeration fluid at conversion pressure in the expansion engine 87 increases as the conversion pressure approaches the critical pressure of hydrogen, practical operating conversion pressures fall within the range of 60 p.
It is to be understood that features of the cycles shown in FIG- URES 1 and 2 may be combined to provide different cycles which may be preferred under certain operating conditions. In particular, a part of the refrigeration fluid withdrawn from the catalytic zone under superatmospheric pressure may be passed in countercurrent heat exchange eflec-ting relation with the high pressure hydrogen gas and warmed to ambient temperature and then compressed from the conversion pressure to the high pressure and recirculated in the cycle in accordance with the arrangement shown in FIGURE 1, while the remaining part of the refrigeration fluid withdrawn from the catalytic zone may be warmed and then expanded with work with the effluent being merged with the countercurrent fiowing low pressure hydrogen vapor of high para concentration according to the arrangement of FIG- URE 2.
The liquefaction and conversion cycle shown in FIG- URE 3 of the drawings includes novel features discussed above in connection with the embodiment of the invention shown in FIGURE 1 together with other novel arrangements and features which make it possible to obtain still greater power savings and to convert hydrogen under any desired pressure.
All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronics, mechanical, photocopying, recording or otherwise, without the prior permission of the authors. Published by Icaris Ltd. Holho 8 00 Praha 8 Czech Republic www. Bondarenko V.
US3095274A - Hydrogen liquefaction and conversion systems - Google Patents
Confirmation of conformity Accreditation field. Electric devices for household use: For cooking and storage of food and mechanization of kitchen work; For handling washing, ironing, drying, cleaning of clothes of shoes; For housekeeping; For maintaining and regulation of microclimate indoors; Sanitary; For hair, nail and skin care; For body warmth; For vibromassage; Gaming, sport and training equipment; Audio and video devices, TV and radio receivers; Sewing and knitting; Power units, charging devices, voltage stabilizers; For gardening; For aquariums and garden reservoirs; Electric pumps; Light equipment and light sources; Wiring devices; Extension cords. Personal electronic computing machines personal computers. Low voltage equipment plugged into personal electronic computing machines.
BINDER KB 23 Benchtop Refrigerated Incubator with Compressor Technology (0.7 cu. ft.)
Income Tax Assessment Act Compilation No. About this compilation. This is a compilation of the Income Tax Effective Life of Depreciating Assets Determination that shows the text of the law as amended and in force on 1 July the compilation date. The notes at the end of this compilation the endnotes include information about amending laws and the amendment history of provisions of the compiled law. Uncommenced amendments. The effect of uncommenced amendments is not shown in the text of the compiled law.
Download: Decree No. Follow us. Ukraine Certification and products compliance. Archive Former national certification systems. Equipment subject to Certification of Compliance are: - turbines - Diesel generators - Devices for lifting operations - conveyors - Chemical equipment, oil and gas - Equipment for the treatment of polymer materials - Pumping equipment pumps, pumping units and facilities - Cryogenic equipment, compressors, refrigeration, autogenous - Gas treatment - Equipment for metal processing - The papermaking equipment - Equipment for geological exploration drilling - Equipment for liquid ammonia - Equipment for the preparation and purification of drinking water - Technological equipment for the foundry industry - trucks - Bicycles except for children - Machines for excavation, land reclamation, development maintenance pits - Etc. The conformity marking " EAC " consists of an acronym. It means that the products certified to be compliant with the essential health and safety requirements of the Technical Regulations in the Custom Union.
Updating K-0.4 and AK-1.5 type of medium-pressure air-fractionating installations
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Customs Union Regulations. Household woodworking machines;. Snow and swamp vehicles, snowmobiles and trailers for them;. Garage equipment for motor vehicles and trailers;. Agricultural machines;. Means of small-scale mechanization of horticultural and forestry applications mechanized, including electric;. Machines for livestock, poultry and feed production;. Power tool, including electric;. Technological equipment for logging, log storage and timber rafting:.
Federal Register of Legislation - Australian Government
Close menu. It is shown that as a result of research, methods have been developed and refined for calculating pressure fluctuations and pipeline and apparatus vibrations and means for damping them; dynamics and strength of plates in self-acting valves; strength and dynamic stability of crankshafts of multibank compressors; economical and reliable control systems; operating processes in cylinders, packings and valves for compressors without lubrication. Show all volumes and issues. Tables of content are generated automatically and are based on records of articles contained that are available in the TIB-Portal index. Due to missing records of articles, the volume display may be incomplete, even though the whole journal is available at TIB. Services for libraries National interlibrary loan International interlibrary loan. Browse subjects Browse through journals Browse through conferences Browse through e-books. Electronic books The e-book database EBC. Help for access and use Terms of access and use Access off campus. Reading desks and facilities Computer workstations Printing — photocopying — scanning Wireless LAN Interactive whiteboards Study cubicles Workstation for the blind and visually impaired.
The List of Products with HS Codes Subject to TR CU 010 Certificate and Declaration
In order to pass the customs and sell the equipment on the territory of the Customs Union, such equipment will require either a declaration or a certificate TR CU The table below indicates all machines and equipment and their HS codes that are subject to this regulation. Snow and swamp walkers, snowmobiles and trailers for them. Garage equipment for motor vehicles and trailers. Small-scale mechanization tools for gardening and forestry use mechanized, including electric. Machines for livestock, poultry and feed production. Mechanized tools, including electric. Technological equipment for logging, timber exchanges and rafting:.
Embodiments disclosed herein relate generally to a process for converting oxygenates to olefins. In one aspect, embodiments disclosed herein relate to a process for converting methanol to olefins MTO.
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