EP4185824A1

EP4185824A1 - Argon enhancing method and device

Info

Publication number: EP4185824A1
Application number: EP20945890.0A
Authority: EP
Inventors: Bowei ZHAO; Fengjie XUE; Alain Briglia
Original assignee: Air Liquide SA; LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Current assignee: Air Liquide SA; LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date: 2020-07-22
Filing date: 2020-07-22
Publication date: 2023-05-31
Also published as: EP4185824A4; WO2022016416A1; US20230296314A1; CN115885146A

Abstract

An air separation apparatus, comprising an air separation unit which comprises a low-pressure column (101), a mixing column (103) and a pure nitrogen column (102), wherein the low-pressure column (101) has a first nominal diameter (D1), the pure nitrogen column (102) has a second nominal diameter (D2) which is smaller than the first nominal diameter (D1), the mixing column (103) has an open cylindrical shape with an interior (129) having an inner diameter (D3) nominally greater than the second nominal diameter (D2), and the pure nitrogen column (102) is located within the interior (129). The mixing column (103) produces additional reflux at the top of the low-pressure column (101).

Description

ARGON ENHANCING METHOD AND DEVICE

Technical Field

The present invention relates to cryogenic air separation process and apparatus, in particular such process and apparatus relating to argon production.

Background

As is well known, double column air distillation plants typically include a medium-pressure distillation column operating at about 6 bars, a low-pressure distillation column operating slightly above atmospheric pressure, and a condenser-vaporizer. After an initial purification, the inlet air is sent to the bottom of the medium-pressure column. A "rich liquid" (air enriched in oxygen) collected in the bottom of the medium-pressure column is sent to reflux at an intermediate point in the low-pressure column. At the same time, the "lean liquid" , consisting almost entirely of nitrogen, collected at the head of the medium-pressure column is sent in reflux at the head of the low-pressure column.
Below the inlet of the rich liquid, the low-pressure column often includes an "argon -tapping" location for the production of this gas. The low-pressure column is generally provided with gaseous oxygen and liquid oxygen withdrawal lines. And the medium-pressure column is generally provided at the head with gaseous nitrogen and liquid nitrogen withdrawal lines. The vapor at the top of the low-pressure column ( "impure nitrogen" ) consists of nitrogen containing a few percent oxygen and is generally released to the atmosphere.
In installations intended essentially to produce gaseous oxygen supplied directly to a user by pipeline, it sometimes happens that the oxygen production can temporarily become surplus. This is particularly the case during periods of shutdown of the end user's factories. In conventional distillation installations the gaseous oxygen is then simply vented into the atmosphere, and the energy expended for the separation of this oxygen is lost.
One solution to this is described in French patent 2550325, which is herein incorporated by reference. The idea of the 2550325 patent is to take advantage of the temporary drop in oxygen demand to increase one or more of the other productions of the installation. Such other productions may be one or more of the productions of argon, liquid oxygen, liquid nitrogen or nitrogen gas.
To this end, the process described in the 2550325 patent utilizes the distillation of air by means of a double column comprising a first distillation column, called a medium-pressure column, operating under a relatively high pressure, and a second distillation column, said low-pressure column, operating under a relatively low-pressure. A liquid withdrawn from one of the two columns is sent to the top of an auxiliary column operating substantially at the pressure of the low-pressure column. A gas less rich in oxygen than this liquid and taken from the low-pressure column is sent to the base of this auxiliary column. The liquid collected at the base of the auxiliary column is sent under reflux into the low-pressure column, substantially at the level of the sampling of said gas. The term "auxiliary column" means a column having the structure of a distillation column, that is to say comprising a lining or a number of trays of the type used in distillation.
Maximum efficiency is obtained when the liquid supplying the auxiliary column is liquid oxygen collected in the bottom of the low-pressure column and said gas is the overhead vapor of this low-pressure column.
Summary
An air separation apparatus is provided, including an air separation unit including a low-pressure column, a mixing column, and a pure nitrogen column, wherein the low-pressure column has a first nominal diameter, the pure nitrogen column has a second nominal diameter which is smaller than the first nominal diameter, wherein the mixing column has an open cylindrical shape, with the inner diameter nominally greater than the second nominal diameter, with the pure nitrogen column located within the mixing column interior.
Brief Description of the Figures
Figure 1 is a schematic representation of one embodiment of the present invention.
Figure 2 is a schematic representation of the upper portion of the distillation column, showing details of the pure nitrogen column and the mixing column, in accordance with one embodiment of the present invention.
Figure 3 is a schematic representation of showing details of the pure nitrogen column and the mixing column, in accordance with one embodiment of the present invention.
Figure 4 is a schematic representation indicating an associated argon column, in accordance with one embodiment of the present invention.
Element Numbers
100 = Process scheme with crude argon column with mixing column concentric to the pure nitrogen column
101 = Low-pressure column
102 = Pure nitrogen column
103 = Mixing column
104 = Sub-cooler
105 = Liquid oxygen pump
106 = Liquid oxygen from LP column
107 = Sub-cooled liquid oxygen
108 = Lean liquid
109 = Sub-cooled lean liquid
110 = Liquid nitrogen
111 = Sub-cooled Liquid nitrogen reflux
112 = Waste nitrogen from low-pressure column
113 = Waste nitrogen to mixing column
114 = Rich oxygen waste from mixing column
115 = Pure nitrogen from pure nitrogen column
116 = Liquid oxygen to storage
117 = Liquid oxygen reflux to mixing column
118 = Rich nitrogen liquid from mixing column
119 = Rich nitrogen liquid from pure nitrogen column
120 = Waste nitrogen to pure nitrogen column
121 = Liquid oxygen reflux valve to mixing column
122 = Lean liquid reflux valve to top of low-pressure column
123 = Waste nitrogen balancing valve
124 = Liquid nitrogen reflux valve to top of pure nitrogen column
125 = Medium-pressure column
127 = Condenser /vaporizer
128 = Feed air inlet
129 = Mixing column interior
130 = distil end of low-pressure column
131 = Combined rich oxygen waste stream from mixing column and waste nitrogen from low-pressure column, before entering sub-cooler.
132 = Combined rich oxygen waste stream from mixing column and waste nitrogen from low-pressure column, after passing through sub-cooler.
133 = Argon column
Description of Embodiments
Illustrative embodiments of the invention are described below. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof have been shown by way of example in the drawings and are herein described in detail. It should be understood, however, that the description herein of specific embodiments is not intended to limit the invention to the particular forms disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
It will of course be appreciated that in the development of any such actual embodiment, numerous implementation-specific decisions must be made to achieve the developer’s specific goals, such as compliance with system-related and business-related constraints, which will vary from one implementation to another. Moreover, it will be appreciated that such a development effort might be complex and time consuming, but would nevertheless be a routine undertaking for those of ordinary skill in the art having the benefit of this disclosure.
The present idea resides in adding a column on the waste nitrogen which will operate in parallel with the pure nitrogen column. This additional column will act as a mixing column which will, with the help of the liquid oxygen reflux sent to the top of this column, produce additional reflux at the top of the low-pressure column.
Turning to Figures 1 through 4, a process scheme with crude argon column with mixing column concentric to the pure nitrogen column 100 is provided. This includes a medium-pressure column 125, a low-pressure column 101, and a condenser-vaporizer 127. Low-pressure column 101 has a first nominal diameter (D1) and a distil end 130. The air to be distilled 128, after being suitably purified (not shown) , is injected into low-pressure column 101 thereby producing a rich liquid consisting almost entirely of oxygen and to an overhead vapor 110 consisting almost entirely of nitrogen.
At least a portion of this overhead vapor is condensed in condenser 127 and collected in column 125. A portion of this lean liquid 108, is subcooled in sub-cooler 104, and then subcooled lean liquid 109 is expanded in lean liquid reflux valve 122 into a pressure slightly above atmospheric pressure. This expanded, sub-cooled liquid is injected substantially at the top of low-pressure column 101 as reflux.
Liquid oxygen 106 is removed from the low-pressure column and is increased in pressure by pump 105, and the pressurized liquid oxygen stream is subcooled in sub-cooler 104. Thus producing sub-cooled liquid oxygen stream 107.
It may happen that, for a limited period of time, the gaseous oxygen becomes surplus, for example due to the temporary shutdown or turndown of a user. In such an instance, sub-cooled liquid oxygen stream 107 may be split into liquid oxygen stream to storage 116, and liquid oxygen reflux stream 117. Pump 105 is adjusted to produce a flow of oxygen in line 117 equal to the excess oxygen.
It has to be noted that the liquid oxygen reflux 117 might also not be sub-cooled in the sub-cooler 104 and then be sent directly to the mixing column 103 from the stream 110.
At the distil end 130 of the low-pressure column is pure nitrogen column 102 and mixing column 103. As indicated in Figure 2, in at least one embodiment, mixing column 103 is concentric with and surrounds pure nitrogen column 102.
Mixing column 103 has an open cylindrical shape, or the shape of a torus with a rectangular cross-section. Mixing column 103 has an interior 129, which has an inner diameter D3. Pure nitrogen column 102 has a second nominal diameter D2. Inner diameter D3 is nominally greater than second nominal diameter D2. This concentric arrangement of mixing column 103 and pure nitrogen column 102 results in lower capital expenditure, since an additional independent pressure vessel is no longer necessary.
During such times of surplus oxygen, liquid oxygen 117, which may pass through liquid oxygen reflux valve 121, is introduced into the top of mixing column 103 and undergoes a countercurrent exchange with the impure nitrogen stream arriving at the bottom of mixing column 103. Mixing column 103 is supplied at the top by liquid oxygen by stream 117. This leads to the evacuation of rich oxygen waste stream 114 and the removal of a rich nitrogen liquid stream 118 consisting of nitrogen containing a few percent of oxygen. Rich oxygen waste stream 114 may be combined with waste nitrogen stream 112 from the low-pressure column, after passing through waste nitrogen balancing valve 123.
The combined rich oxygen waste stream 114 and waste nitrogen stream 112 may then be introduced into argon column 133. At least a portion of the combined stream 131 may be introduced into argon column 133 prior to having passed through sub-cooler 104. At least a portion of the combined stream 132 may be introduced into argon column 133 after having passed through sub-cooler 104.
The double column 125 /101 is equipped with an additional column 102, called a "minaret" , or pure nitrogen column, for the production of pure nitrogen under low-pressure. Column 102 is supplied at the bottom with impure nitrogen 120, and at the top. by the sub-cooled liquid nitrogen reflux 111 taken from the top of the column 125, by conduit 110, sub-cooled in sub-cooler 104 and controlled a liquid nitrogen reflux valve 124. The pure nitrogen leaves at the head of the column 102 by conduit 115, and rich nitrogen liquid 119 is removed from the bottom of pure nitrogen column 102.

Claims

An air separation apparatus, comprising;

· an air separation unit comprising a low-pressure column (101) , a mixing column (103) , and a pure nitrogen column (102) ,

· wherein the low-pressure column (101) has a first nominal diameter (D1) , the pure nitrogen column (102) has a second nominal diameter (D2) which is smaller than the first nominal diameter (D1) ,

· wherein the mixing column (103) has an open cylindrical shape, with an interior (129) having an inner diameter (D3) nominally greater than the second nominal diameter (D2) , with the pure nitrogen column (102) located within the mixing column interior (129) .
The apparatus of claim 1, wherein the mixing column (103) and the pure nitrogen column (102) are in fluidic contact with a distil end (130) of the low-pressure column (101) .
The apparatus of claim 1 or 2, wherein the mixing column (103) is configured to:

· receive liquid oxygen reflux (117) ,

· produce rich oxygen waste (114) ,

· receive waste nitrogen (113) from the low-pressure column (101) , and

· return rich liquid (118) to the low-pressure column (101) .
The apparatus of claim 1 or 2, wherein the pure nitrogen column (102) is configured to:

· receive sub-cooled liquid nitrogen reflux (111) ,

· produce pure nitrogen (115) ,

· receive waste nitrogen (120) from the low-pressure column (101) , and

· return rich nitrogen liquid (119) to the low-pressure column (101) .
A process for enhanced Argon recovery, comprising:

· an air separation unit comprising a low-pressure column (101) , a mixing column (103) , and a pure nitrogen column (102) , wherein the low-pressure column (101) has a first nominal diameter (D1) , the pure nitrogen column (102) has a second nominal diameter (D2) which is smaller than the first nominal diameter (D1) ,

· wherein the mixing column (103) has an open cylindrical shape, with an interior (129) having an inner diameter (D3) nominally greater than the second nominal diameter (D2) , with the pure nitrogen column (102) located within the mixing column interior (129)

· wherein the mixing column (103) and the pure nitrogen column (102) are in fluidic contact with a distil end (130) of the low-pressure column (101) ,

· wherein the mixing column (103) :

ο receives a liquid oxygen reflux stream (117) ,

ο produces a rich oxygen waste stream (114) ,

ο receives a waste nitrogen stream (113) from the low-pressure column (101) , and

ο returns a rich liquid stream (118) to the low-pressure column (101) ,

· wherein the pure nitrogen column (102) :

ο receives a sub-cooled liquid nitrogen reflux stream (111) ,

ο produces a pure nitrogen stream (115) ,

ο receives a waste nitrogen stream (119) from the low-pressure column (101) , and

ο returns a rich nitrogen liquid stream (102) to the low-pressure column (101) ,

· wherein the rich oxygen waste stream (114) and a waste nitrogen stream (112) from the low-pressure column (101) are introduced into an argon column (133) .