CN109925739A - A kind of process of the ammonia nitrogen purification of ATR conversion gas - Google Patents
A kind of process of the ammonia nitrogen purification of ATR conversion gas Download PDFInfo
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- CN109925739A CN109925739A CN201910283179.9A CN201910283179A CN109925739A CN 109925739 A CN109925739 A CN 109925739A CN 201910283179 A CN201910283179 A CN 201910283179A CN 109925739 A CN109925739 A CN 109925739A
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Abstract
The invention discloses a kind of processes of the ammonia nitrogen purification of ATR conversion gas, after ATR conversion gas is entered fractional condensation tank progress gas-liquid separation, the gas phase of the impurity containing ammonia nitrogen left enters scrubbing tower, the waste water being discharged from fractional condensation tank and scrubbing tower is contacted through stripper with steam counter-flow, the higher steam of ammonia-nitrogen content goes out from stripper top row, ammonia-nitrogen content drops to 100ppm waste water below and is discharged from stripper tower bottom, sewage network is accessed after cooling, process operation parameter is as follows: 4 pieces of the theoretical plate of scrubbing tower, diameter 1.4m, tower height 4m, filler is Pall ring Dg38, the high 0.998m of filler, absorbent is water, absorbent dosage is 2m3/h；8 pieces, diameter 0.6m of the theoretical plate of stripper, the high 3m of filler, filler is Pall ring Dg38.
Description
Technical field
The invention belongs to methanol ATR to convert gas purification process, be related to a kind of technique side of the ammonia nitrogen purification of ATR conversion gas
Method.
Background technique
With the development of China's Chemical Engineering Technology, methanol has been widely applied to other as a kind of common, important raw material
In the production of chemical products, China has become the first in the world methanol production state.The synthetic technology of methanol is highly developed reliable, mesh
It is preceding main to use using coal or natural gas as waste synthetic gas CO and H2Method synthesis.Before carrying out synthetic reaction,
Want first producing synthesis gas, the quality of the relationship between quality of synthesis gas to methanol product, thus before synthetic reaction synthesis gas it is miscellaneous
Matter content must be strictly controlled.
The quality of synthesis gas is mainly related with following several impurity on the basis of meeting methanol-fueled CLC hydrogen-carbon ratio: ash content,
Hydrogen sulfide (H2S), oxygen (O2), nitrogen (N2) and argon (Ar) etc..And nitrogen can react in process system with hydrogen, generate
Micro ammonia, micro ammonia can further generate monomethyl amine, dimethylamine, trimethylamine in system for methanol synthesis has product methanol
There is peculiar stink.Reflect according to factory technician, the methanol product of rectification section has fish bad smell, through to ATR, (natural gas is certainly
Thermal reforming) reburner send out conversion gas carry out analysis find wherein really contain micro ammonia, set forth herein in ATR transformation system
The removing means of a set of ammonia nitrogen compound is concatenated after system with decontaminating syngas, it is intended to Ammonia in research removing ATR conversion gas
Technology establishes ammonia nitrogen purification process process and seeks suitable process and device parameter.
Summary of the invention
In view of this, the present invention provides a kind of process of the ammonia nitrogen purification of ATR conversion gas.
The present invention specifically provides the following technical solution: a kind of process of the ammonia nitrogen purification of ATR conversion gas, will
ATR conversion gas enter fractional condensation tank carry out gas-liquid separation after, the gas phase of the impurity containing ammonia nitrogen left enters scrubbing tower, from fractional condensation tank and
The waste water of scrubbing tower discharge is contacted through stripper with steam counter-flow, and the higher steam of ammonia-nitrogen content goes out from stripper top row, ammonia nitrogen
Content drops to 100ppm waste water below and is discharged from stripper tower bottom, is cooled to 38~43 DEG C of access sewage networks, technique behaviour
It is as follows to make parameter:
Further, the steam usage amount of the stripper is 1500Kg/h.
Further, the outlet pressure of fractional condensation tank (2) is set as 2.44MPa；The outlet pressure of the scrubbing tower (3) is set
It is set to 2.42MPa；The tower top pressure of stripper (6) is set as 0.2MPa.
Further, the composition of the ATR conversion gas is calculated as by molar fraction:
The beneficial effects of the present invention are:
(1) present invention passes through Aspen Plus simulation pair for the ammonia nitrogen purification process process of ATR conversion gas (synthesis gas)
Flow process parameter is verified, and according to the actual requirement of cooperative factory, has adjusted device parameter, and carry out to device parameter
It checks.It solves the problems, such as to increase containing methanol rectification load caused by ammonia synthesis gas and product methanol is frowzy.
(2) technical process scheme of the invention shows in nearly 3 years operational process so far after implementing engineering
Steadily, the decontamination index and actual motion state for simulating calculating are identical, and the taste disappearance of product methanol confirms the technology
Feasibility.
(3) ammonia-nitrogen content in waste water is dropped into 100PPm hereinafter, the technical process established can effectively remove synthesis gas
In ammonia, have extraordinary absorbability, and ammonia-containing water can be carried out concentration and recovery by stripping process.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing:
Fig. 1 is that ATR converts gas ammonia nitrogen purification process flow chart: 1- segregates tank entrance cooler, and 2- segregates tank, 3- washing
Tower, 4- gaseous effluent cooler, 5- tower bottom cooler, 6- stripper, 7- stripper condenser, 8- ammonium hydroxide surge tank
Fig. 2 design pattern scrubbing tower gas-liquid load figure；
Fig. 3 checks mode scrubbing tower gas-liquid load figure；
Fig. 4 design pattern stripper gas-liquid load figure；
Fig. 5 checks mode stripper gas-liquid load figure.
Specific embodiment
With reference to the accompanying drawing, a preferred embodiment of the present invention will be described in detail.
Embodiment 1
(1) determination of analogy method
In the modeling process to synthesis gas ammonia nitrogen purification process process, suitable thermodynamical model and physical property method are selected
It is the basis that ammonia nitrogen purification process correctly models.For the simulation meter for the ammonia nitrogen purification process that washing unit and steam stripping unit are set up
Calculate, need a large amount of thermodynamic analysis, it is also necessary to the gas-liquid phase equilibrium of model, normalization, material balance, energy balance etc. into
The complicated operation of row, while being also to establish correct mould to accurately calculating for gas-liquid phase concentration, density, braised value, temperature etc. in model
The necessary condition of type.The calculating of ammonia nitrogen purification process is actually the calculating that a multistage balances each other.For washing and stripping
The calculating of unit whether calculate accurately, depending on calculate the method that balances each other whether select it is proper.
By thermodynamical model needed for the purification of analysis mode synthesis gas ammonia nitrogen, H compared2O-CO2And H2O-NH3System
Vapor liquid equilibrium data, after comparison, synthesis gas ammonia nitrogen purification process using Aspen Plus ELECNRTL thermodynamical model into
Row simulation calculates.
(2) process engineering models
ATR conversion gas ammonia nitrogen purification process steady-state model is established using Aspen Plus, as shown in Figure 1.ATR conversion air cooling
But after entering fractional condensation tank progress gas-liquid separation to 40 DEG C or so, the gas phase left enters scrubbing tower boiler water washing, obtains net
The ATR conversion gas of change removes downstream process.The waste water being discharged from fractional condensation tank and scrubbing tower is contacted through stripper with steam counter-flow, will be given up
Ammonia nitrogen substances in water steam, and the higher steam of ammonia-nitrogen content, which goes out after condensing to send to out-of-bounds company from stripper top row, to be handled.
Ammonia-nitrogen content drop to 100ppm waste water below from stripper tower bottom discharge be cooled to 40 DEG C or so nearby access workshops it is existing
Sewage network.
(3) input data and basic technological parameters
The actual ATR conversion gas composition of factory is as follows:
1 ATR of table converts gas composition (molar fraction)
The flow that ATR converts gas is 2750.8kmol/h, and before entering fractional condensation tank, temperature is 128 DEG C, and pressure is
2.48MPa.It is the initial process data of each unit below it is required that reaching 14.5 ton/hours of waste treatment capacity.
Fractional condensation tank entrance cooler (1) outlet temperature is set as 40 DEG C, and outlet pressure is set as 2.45MPa；
Fractional condensation tank (2) sets outlet pressure as 2.44MPa, adiabatic flash；
Scrubbing tower (3) outlet pressure is set as 2.42MPa；
Stripper (6) tower top pressure is set as 0.2MPa；
Stripper condenser (7) outlet temperature is set as 40 DEG C, and pressure is set to 0.15MPa；
Tower bottom cooler (5) outlet temperature is set as 40 DEG C, and pressure is set as 0.13MPa；
Ammonium hydroxide surge tank (8) outlet pressure is set as 0.13MPa, and operating condition is assumed to adiabatic flash；
Pump equipment does not embody in process simulation, and the supply temperature of cooling circulating water is 33 DEG C, and supply pressure is
0.42MPa；Return pipe net pressure is 0.3MPa, and temperature is 43 DEG C.The steam pressure of supply is 0.55MPa, and temperature is 210 DEG C.
Wash boiler water pressure is 9.5MPa, and temperature is 40 DEG C.
(4) determination of absorbent dosage
In the art, since ammonia is highly soluble in water, the absorbent of scrubbing tower uses water.Under the conditions of already known processes, first
Seeking minimal absorption agent water consumption is 8.6kmol/h, and the pre-selection of flood point is carried out by Eckert common relative graph, due to inhaling
It is unknown to receive dosage WL, can only first assume that a series of absorbent dosage carries out tentative calculation.Calculating process is as follows:
Abscissa calculation formula:
Ordinate calculation formula:
Here Fillers selection Pall ring Dg38, packing factor 130m-1, flow transitivity parameter therein is by Aspen
It is obtained after process before Plus simulation scrubbing tower.From 1.2 times of 8.6Kmol/h absorbent dosage, i.e. the dosage of 186Kg/h starts to count
It calculates.
Examination difference obtains flood point substantially in 1.12m/s.If by its 80% consideration, tower diameter 0.98m, but due to the factory
Capacity expansion revamping is being carried out, tolerance future may further increase.Therefore for the sake of guarding, flood point line presses 100Pa/m pressure
It drops line to consider, take the 60% of its load, gas velocity is about 0.8m/s at this time, and being computed tower diameter is 1.34m, in flowsheeting below
In, hydraulics check will be carried out by the tower diameter of rounding to 1.4m.The determination of absorbent dosage will meet absorption and require, and ATR turns
Change gas wherein NH after absorption3Concentration is less than 1ppm hereinafter, also to consider that the hydraulic performance of tower and subsequent device operation are negative
Lotus.
Scrubbing tower primary condition in the present invention uses only less theoretical plate and calculates.
Scrubbing tower tower diameter calculated is 1.4m in the present invention, if the dumped packing for selecting diameter to be no more than 75mm, be can use
Minimum wetting rate (LW) min is 0.08m3/(m·h).The specific surface of Dg38 Pall ring is 146m2/m3
Minimum spray density Umin=0.08 × 146=11.68m3/(m·h)
Cause
Solving the smallest spray flow Lmin is 17.97m3/h.If but operated using the spray flow as actual spray, it can shadow
The boiler water rung to rear end other processes is supplied, while the water can be such that the load of stripper greatly increases.In 1 piece of theoretical plate
In the case of, the situation of change of ammonia density is exported by sensitivity analysis, discovery singly balanced grade absorbent used in amounts reaches about 5m3/h
NH just may be implemented3The requirement of exit concentration, but the desalted water deliverability of actually factory site is limited, it can only be in 5m3/ h with
Interior supply.For this purpose, technique requirement can only be reached using more theoretical plates.
(5) determination of scrubbing tower theoretical cam curve
Under conditions of certain absorbent water consumption, by changing the theoretical cam curve of scrubbing tower, analysis ATR converts gas
Export NH3The variation tendency of concentration.The NH of the more scrubbing tower outlets of theoretical cam curve3Content is lower, but the investment of equipment will be more
It is high.NH in gas is converted by analyzing absorbent dosage and ATR under different theoretical plates3The relationship of concentration considers under 1.4m tower diameter
The performance of filler plays, using 4 pieces of theoretical plates and 2m3The condition of/h absorbent carries out sunykatuib analysis.
(6) determination of stripper technological parameter
The effect of stripper is by the NH in absorbent water3It steams and is concentrated, then send outside, which adopts to reduce investment outlay
With the technique of steam Direct Contact Heating, stripper is passed through water sealed tank using absolute pressure 0.2MPa operation convenient for exhaust gas, and tower top is adopted
Cooling with recirculated cooling water, condenser temperature is sent outside after need to controlling the liquid separation fixed gas condensed out at < 40 DEG C to technique
Waste water pipe network is handled.It is cold through cooler after a large amount of waste water of stripper tower bottom discharge are used to preheat waste water streams to be processed
But it to after 40 DEG C, is discharged into the general waste water pipe network of full factory and is handled.The ammonia density that plant requirements enter general waste water pipe network wants small
In 100ppm.
In first block of plate, no reflux only needs excellent the stripper feed entrance point without reboiler in the case where theoretical plate is certain
Change optimal steam addition.Therefore, the method being used in combination by the design code and sensitivity analysis of Aspen Plus into
Variation tendency below has been calculated in row simulation.Constraint condition is that tower bottom nitrogenous compound concentration is equal to 0.0001, and steam is
208 DEG C, pressure 4.5bar.
With under the design condition of 5 pieces of theoretical plates, with the hydraulics of 1.2 times of consideration towers of steam consumption 1772.95Kg/h
Design.In order to save purchase cost, the same Pall ring for choosing Dg38 carries out tentative calculation.
Abscissa calculation formula:
Ordinate calculation formula:
It is 2.25m/s that flood point, which is calculated, is calculated by its 60% flood point, tower diameter 0.6m.With the condition
Optimize final theoretical cam curve, the height equivalent to one theoretical plate (HETP) of the Dg38 metal Pall ring provided by filler supplier is about 500mm, filler
Unit price is 6000 yuan/m3, steam price be 200 yuan/ton optimize, the investment payback time be 3 years consider.Total cost is stripper
Year the sum of cost of equipment and year operating cost.The accounting of operating cost is lower in 3 years, and cost of equipment is very sensitive to tower diameter.If
The equipment cycle of operation increases, it is anticipated that the accounting of operating cost will be gradually increased, and make the reduction of cost of equipment accounting.But it is overall next
It sees, the cost of equipment reduction that is conducive to overall expenses as far as possible.The equipment stripper is in the feelings for considering certain operation surplus
Under condition, select with 8 pieces of theoretical plates, the tower diameter of 0.6m is designed, and steam usage amount is determined as 1500Kg/h.It is calculated through simulation
Ammonia density can be reduced to 80ppm in waste water.
(8) determination of scrubbing tower diameter and tower height
The operating pressure that scrubbing tower is set passes through the Column Internal module meter in Aspen Plus as 2.42MPa
It calculates, device diameters are still pressed 1.4m due to the production capacity demand in factory's future and considered in 1.0m or so.Calculating process is as follows:
Aspen Plus recommend tower diameter in 1.03m, following Fig. 2 of gas-liquid load situation of the 3rd piece of theoretical plate, figure it is seen that
Under the tower diameter of 1.03m, within allowed band, filler can work normally operating point.As shown in figure 3, by tower diameter adjust to
After 1.4m, operating point still works in the normal range, but the performance of filler is not played well.In the condition of 1.4m
Under, by the way that the computation model of scrubbing tower is revised as the calculating that Rate-based carries out tower height.It is worth noting that, using
When Rate-based calculates packed tower, in the number of plates of the configuration Configuration at the interface Setup of RadFrac
It is no longer number of theoretical plate, but the segments of integral calculation, increase integral calculation under the premise of guaranteeing convergent as far as possible
Number of segment.Finally, the present invention has taken 60 sections of integral to be segmented, although further segmentation remains to make the outlet NH3 in ATR conversion gas
Concentration decline, but unnecessarily, calculating speed at this time is very slow.The result shows that HETP=0.998m, when 4 pieces of theoretical plates
Tower height needs 3.6m, and the bed stuffing height of rounding to 4m, the ammonia density in ATR conversion gas at this time is 0.8ppm.
(9) determination of stripper packed height
It, can also be using filler as gas-liquid mass transfer component since the diameter of stripper is smaller.In order to reduce buying filler
Cost, also calculated using Dg38 Pall ring, calculate tower height degree.Under design pattern, the Column of Aspen Plus
The tower diameter that Internals module provides is 0.577m.
Under 0.577m diameter, the operating point of tower packing is analyzed by taking the 4th piece of theoretical plate as an example: such as Fig. 4, by stripper apparatus
Diameter rounding simulates its operating point to 0.6m, and height needed for calculating filler.Stripper operating point such as Fig. 5 of 0.6m diameter:
It is Rate-based that the simulation of stripper, which is calculated schema modification, in order to calculate tower height.Stripper is cut into 25 sections, is passed through
HETP is between 0.31m to 0.4m for simulation discovery.Therefore, 8 pieces of theoretical plates are equivalent to the filler tower height of 2.85m.It is found after accounting
It is suitable with the outlet waste water ammonia density of balance model, it is 72ppm.Final packed height rounding is to 3.0m.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (4)
1. a kind of process of the ammonia nitrogen purification of ATR conversion gas, which is characterized in that by ATR conversion gas enter fractional condensation tank (2) into
After row gas-liquid separation, the gas phase of the impurity containing ammonia nitrogen left enters scrubbing tower (3), is discharged from fractional condensation tank (2) and scrubbing tower (3)
Waste water is contacted through stripper (6) with steam counter-flow, and the higher steam of ammonia-nitrogen content goes out from stripper top row, and ammonia-nitrogen content drops to
100ppm waste water below is discharged from stripper tower bottom, accesses sewage network after cooling, process operation parameter is as follows:
2. a kind of process of the ammonia nitrogen purification of ATR conversion gas according to claim 1, it is characterised in that: the vapour
The steam usage amount of stripper is 1500Kg/h.
3. a kind of process of the ammonia nitrogen purification of ATR conversion gas according to claim 1, it is characterised in that: described point
The outlet pressure of solidifying tank (2) is set as 2.44MPa；The outlet pressure of the scrubbing tower (3) is set as 2.42MPa；Stripper (6)
Tower top pressure be set as 0.2MPa.
4. a kind of process of the ammonia nitrogen purification of ATR conversion gas according to claim 1, it is characterised in that: the ATR
The composition of conversion gas is calculated as by molar fraction:
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675336A (en) * | 2002-08-06 | 2005-09-28 | 三菱重工业株式会社 | Wet gas purification method and system for practicing the same |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1675336A (en) * | 2002-08-06 | 2005-09-28 | 三菱重工业株式会社 | Wet gas purification method and system for practicing the same |
Non-Patent Citations (3)
| Title |
|---|
| 张祉祐等: "《低温技术原理与装置（下册）》", 30 November 1987, 机械工业出版社 * |
| 申奕: "《化工单元操作技术》", 30 June 2009, 天津大学出版社 * |
| 赖奇等: "《化工模拟 Aspen教程》", 31 January 2017, 北京理工大学出版社 * |
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Application publication date: 20190625 |