CN106582272B - The desulfurizing and purifying technique of sour water stripping ammonia - Google Patents

The desulfurizing and purifying technique of sour water stripping ammonia Download PDF

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CN106582272B
CN106582272B CN201611149118.6A CN201611149118A CN106582272B CN 106582272 B CN106582272 B CN 106582272B CN 201611149118 A CN201611149118 A CN 201611149118A CN 106582272 B CN106582272 B CN 106582272B
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desulfurizing
ammonia
purifying
sulfur
quinones
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CN106582272A (en
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杨金帅
崔国栋
胡文宾
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SHANDONG XUNDA CHEMICAL GROUP CO Ltd
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SHANDONG XUNDA CHEMICAL GROUP CO Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0423—Beds in columns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/0407—Constructional details of adsorbing systems
    • B01D53/0438—Cooling or heating systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76—Gas phase processes, e.g. by using aerosols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/40—Further details for adsorption processes and devices
    • B01D2259/40083—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption
    • B01D2259/40086—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by using a purge gas

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Industrial Gases (AREA)

Abstract

The present invention provides a kind of desulfurizing and purifying technique of sour water stripping ammonia, and capital equipment includes two catalysis oxidations that can be series-parallel absorption desulfurizing and purifying towers, filling can hot recycling desulfurizing decontaminating agent, set heat exchanger tube in bed；10-60 DEG C of operation temperature, H in ammonia after processing2S≤3ug/g, SO2≤ 3ug/g, organic sulfur≤3ug/g are substantially free of phenol/quinones, cyanogen class, hydro carbons；When desulfurizing and purifying tower hot recycling, the elemental sulfur for adsorbing deposition is condensed into liquid sulfur recovery, contains organic sulfur, phenol/quinones, cyanogen class, hydrocarbon, NH3、CO2Exhaust gas be incorporated to stripper overhead richness H2S gas pipeline, goes combustion furnace of sulfur recovery device to handle, or goes burn-up to empty into flare line.

Description

The desulfurizing and purifying technique of sour water stripping ammonia
Technical field
The present invention relates to a kind of ammonia decontamination purifying techniques, and in particular to a kind of desulfurizing and purifying of sour water stripping ammonia Technique.
Background technique
Oil plant, coal plant, coking of coal factory, sour water caused by natural gas from coal factory, are separated by stripping, can Obtain hydrogen sulfide air-flow and ammonia air-flow.
Sour water strips in separating obtained ammonia, separates such as sour water Single-tower stripping and condenses gained ammonia through three-level Gas usually contains the H such as 1% or so2S, generally through recycling washing method for most of H2S washes ammonium hydroxide and returns stripper to be divided again From, or it is made into NH4HS crystalline product or solution are sold, or are directly down to low temperature without ammonia scrubbing and are formed NH4HS crystallization will be big Part H2S is removed；Remaining a small amount of H in ammonia2S passes through desulfurizing agent adsorption treatment again, and ammonia can reach H after processing2S≤10ug/ The level of g or even≤3ug/g.
In some sour water occasions, gained ammonia main component such as NH398-99% or so, hydrogen sulfide 0.7% or so, but Contained organic sulfur, volatile phenol/quinones, cyanogen class, hydro carbons are more, and smell component is more, handle through the above method, gained NH4HS knot Brilliant or solution there are color, peculiar smell and impurity, purity problem and purposes is limited or can not sell, use；Desulfurizing agent is to contained Organic sulfur such as COS, mercaptan, thioether, CS2And volatile phenol/quinones, cyanogen class, without clean-up effect or not ideal enough, sometimes The etching problem of ammonia following process equipment such as compressor is caused, there is also colors, contaminant problem for prepared ammonium hydroxide or liquefied ammonia；Essence What is be discharged when desulfurizer regeneration contains organic sulfur, volatile phenol/quinones, cyanogen class exhaust gas, usually torch burning is sent to empty, and torch pair The combustion efficiency of this kind of exhaust gas is general, often remaining significantly peculiar smell and pollution.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of desulfurizing and purifying technique of sour water stripping ammonia, along ammonia Air-flow includes two catalysis oxidation that can be series-parallel absorption desulfurizing and purifying towers to capital equipment, and setting can fill in desulfurizing and purifying tower Divide the heat exchanger tube of drop mild heat desulfurizing agent bed, desulfurizing and purifying tower lower part outlet connection regeneration condenser regenerates condenser bottom Portion has the sulfur outlet that liquid elemental sulfur can be accomplished continuously or intermittently discharged but gas is not discharged；
Ammonia is incorporated oxygen and is mixed well before entering absorption desulfurizing and purifying tower, the amount of allocating of oxygen is slightly more than and vulcanization O needed for object reaction generates elemental sulfur2Amount, the sulfide concentration on-line determination in ammonia；
Adsorb desulfurizing and purifying tower filling can hot recycling catalytic oxidation adsorption desulfurizer, 10-60 DEG C of operation temperature, by ammonia Contained a small amount of organic sulfur, phenol/quinones, cyanogen class, hydro carbons absorption, by contained minute quantity SO2With contained H2S reaction is converted into elemental sulfur And adsorb, by remaining H2S is oxidized to elemental sulfur and is adsorbed in inner hole between particle；H in ammonia after processing2S≤3ug/g, SO2≤ 3ug/g, organic sulfur≤3ug/g are substantially free of phenol/quinones, cyanogen class, hydro carbons；
Desulfurizing and purifying tower operates after sulfide, phenol/quinones, cyanogen class, one of hydro carbons into outlet ammonia be more than specified value, Desulfurizing and purifying tower cuts out elemental sulfur, the sulfide, phenol/quinones, cyanogen class, hydro carbons for carrying out hot recycling blowing absorption deposition；Hot recycling When the material, the gas that are discharged enter regeneration condenser, wherein molten sulfur and sulfur vapor are condensed into liquid sulfur, solid-state sulfur recovery, containing organic sulfur, Phenol/quinones, cyanogen class, hydrocarbon, NH3、CO2Exhaust gas be incorporated to stripper overhead richness H2S gas pipeline, goes at combustion furnace of sulfur recovery device Reason, or go burn-up to empty into flare line.
It is described can hot recycling catalytic oxidation adsorption desulfurizer, can be by activated carbon supported Fe, Mn, Cu, Zn, Co etc. at Divide the catalytic oxidation adsorption desulfurizer of modified preparation, the Sulfur capacity with >=20% (quality), and the H of≤1ug/L2S removes precision, It is preferred that the catalytic oxidation adsorption desulfurizer with tempreture organic sulphur hydrolysis conversion removing ability, can also will have higher H2S removing is held Amount is arranged in pairs or groups and is used with the desulfurizing agent of precision and the desulfurizing agent with tempreture organic sulphur hydrolysis conversion removing ability, described to have organic sulfur water The desulfurizing agent of solution conversion removing ability can also restore substantially its performance by hot recycling, to improve COS, CS2, mercaptan etc. penetrates Time, wherein COS is hydrolyzed to H2S is simultaneously further oxidized to elemental sulfur absorption deposition removing, and mercaptan is converted into that molecular weight is bigger, inhales The bigger disulphide of attached amount, the disulphide can also be blown away during hot recycling, to improve absorption desulfurizing and purifying Tower accommodates the ability of organic sulfur before penetrating.The specific surface area of absorbent charcoal carrier is very big, has a large amount of hydrophobic groups, has to most of Machine sulphur, phenol/quinones, cyanogen class, hydro carbons have stronger adsorption capacity,
For ammonia in the decontamination process of absorption desulfurizing and purifying tower, key reaction is H2S、O2Reaction generates elemental sulfur, should Reaction has heat release, every 1% volume H2S matches aequum O2The adiabatic temperature rise that reaction generates elemental sulfur is 60 DEG C or so, desulfurizing agent bed The purpose of middle setting heat exchanger tube and water cooling is to avoid bed temperature from rising to decline with caused absorption property；In ammonia containing organic When sulphur, phenol/quinones, cyanogen class, hydrocarbon are more, desulfurizing and purifying tower should use operation temperature appropriate, take into account the hydrolysis of organic sulfur With the absorption of residual organic sulfur, phenol/quinones, cyanogen class, hydrocarbon, experience is 40-50 DEG C or so preferable.
Heat exchange in desulfurizing and purifying tower, except common spiral coil can be used, it is preferred to use vertical pipes heat exchange structure, The bed temperature difference is small when advantage is mainly desulfurizing and purifying, is easy temperature control, and the heating higher than bed temperature permissible value can be used in when regeneration Medium temperature is easy when leakage to stop a leak by shutting one or a few casing, is easy to unload agent when desulfurizing decontaminating agent is scrapped.
The desulfurizing and purifying tower with vertical pipes heat exchange structure, the cooling water for using temperature slightly lower as move thermal medium, Water inlet, draining and its distribution into casing, from collecting in casing, be all disposed within intake chamber, the row of desulfurizing and purifying top of tower Water chamber；Casing extends down into desulfurizing decontaminating agent bed, until desulfurizing decontaminating agent bed bottom, desulfurizing decontaminating agent bed it Lower filling inert ceramic balls are as support, and the quantity and heat exchange area of heat exchange sleeve are enough, to guarantee exchange capability of heat；It is described vertical Casing is formed by inner and outer tubes nesting, and inner tube, the upper port of outer tube are separately connected intake chamber, drip chamber, end closure under outer tube, Inner tube lower end extends to outer tube lower end and is open, inner tube water to flow down, outer tube water Xiang Shangliu, inner tube, outer tube water, carbonated drink stream To being formed by cooling water circulating pump power；Pass through the entrance of control cooling water, the temperature difference of discharge and the shifting of flow or casing Thermal energy power can preferably control bed temperature when desulfurizing decontaminating agent normal operating, reach the degree of the small temperature difference, easy temperature control.By Preferable in 40-50 DEG C of desulfurizing decontaminating agent bed temperature, controlling 30 DEG C of cooling water inlet temperature or so, 40 DEG C of temperature at discharging condensate or so is Can, in addition to directlying adopt the common recirculated water of plant area as cooling water, it can also separately set cooling water heat exchanger and be followed with plant area is common The advantages of ring water gives indirect heat exchange, indirect heat exchange is that cooling water is easy discovery when leaking into ammonia or ammonia inleakage of cooling water, also Pure water can be used or deionized water does cooling water.
When desulfurizing and purifying tower uses above-mentioned vertical pipes heat exchange structure, there is also heat exchanges between inner and outer tubes, this is Its feature for being different from spiral coil.In the premise that cooling water flow is identical, out temperature is all respectively 35 DEG C, 45 DEG C Under, when inner tube water flow to outer pipe bottom and started cooling effect, temperature has had been raised to 39 DEG C, it is clear that bed obtained The temperature difference is smaller；Such case is more significant in desulfurizing agent hot recycling, can especially use in desulfurizing agent bed temperature-rise period Higher heating medium inlet temperature.
In the desulfurizing and purifying tower with vertical pipes heat exchange structure, the vertical water cold sleeve should have appropriate Away from heat exchange area, move thermal energy power, especially should use same casing size and spacing as far as possible in ammonia entrance, to prevent surpass Temperature.Heat exchange sleeve gos deep into the height 0.5-10m of desulfurizing decontaminating agent bed, tube spacing 0.05-0.10m, heat exchange area 5-30m2/m3 Desulfurizing decontaminating agent.The positions and dimensions of desulfurizing decontaminating agent filling pipe should be appropriately arranged with, and avoid the spacing for influencing to close on heat exchange sleeve, Guarantee that the desulfurizing decontaminating agent bed temperature below desulfurizing decontaminating agent filling pipe meets the requirements.
The structure of the desulfurizing and purifying tower desulfurizing decontaminating agent bed can be axially or radially according to ammonia flow direction, the reaction The structure of device is easier to draw off from reactor bottom when desulfurizing decontaminating agent can be made to scrap, and new agent is filled from reactor head or upper lateral part It fills out.Wherein the axial arrangement of ammonia upper entering and lower leaving is preferable, the reason is that H2S and O2Reaction speed quickly, is reacted and heat release region collection In, each vertical pipes water cooling all plays shifting heat effect at any time when axial arrangement, thus temperature control and reaction effect are more preferable.
As H in outlet ammonia or subsequent ammonia product2S, one of organic sulfur, phenol/quinones, cyanogen class, hydrocarbon are close to specified value When, absorption desulfurizing and purifying tower carries out hot recycling process.It, can be first with nitrogen by the ammonia in desulfurizing and purifying tower before desulfurizing agent hot recycling It is absorbed in sour water before being purged to stripper entrance, but should take appropriate measures and be such as incorporated before being passed through sour water Air or nitrogen prevent sour water from quickly inhaling ammonia and flowing backwards and enter desulfurizing and purifying tower, or is slowly blown into suitable tower in stripper Board position；And the water in water chamber, drip chamber, casing heat-tranferring system is released, blowout.
250-300 DEG C of the hot regeneration temperature of desulfurizing and purifying tower.During hot recycling, to water chamber be passed through 250-350 DEG C plus Thermal medium such as hot wind, steam or conduction oil, using higher heat carrier temperature when desulfurizing decontaminating agent bed temperature is lower, later It gradually decreases；Heat medium from top to bottom, then from outer tube from bottom to top returns to drip chamber from the inner tube of casing, gradually that desulfurization is net Agent bed heats, and most of absorption in desulfurizing decontaminating agent bed is deposited into branch's fusing, vaporization, flows through again from lower part outlet Raw and cold condenser is collected and condensation elemental sulfur, contains organic sulfur, phenol/quinones, cyanogen class, hydrocarbon, NH3、CO2Exhaust gas be incorporated to stripper overhead Rich H2S gas pipeline, goes combustion furnace of sulfur recovery device to handle, and burn-up can also be gone to empty into flare line.During hot recycling to Nitrogen is passed through in desulfurizing decontaminating agent bed, carbon dioxide is continuously purged, will desorption object blowout, further empty surface and interior Desulfurizing and purifying performance is restored in hole.Water chamber after the completion of hot recycling, drip chamber can lead to cooling water in casing heat-tranferring system and be down to 40 DEG C It is stand-by below or come into operation, if it is necessary, can be replaced with purified ammonia before coming into operation, send to stripper after ammonia displacement It is absorbed in sour water before mouthful, but should take appropriate measures and be incorporated air or nitrogen such as before being passed through sour water, prevented Only sour water, which is quickly inhaled ammonia and flow backwards, enters desulfurizing and purifying tower；Or slowly it is blown into suitable tray location in stripper.
In the present invention, condenser is regenerated, preferably there is somewhat larger inner space and heat exchange tube spacing, hot material inlet First half can condensing trapping liquid sulfur, the latter half of waste gas outlet further can condense to form solid-state sulphur, pass through by Cooling water flow carries out height weave control appropriate, and the solid-state sulphur interval that latter half cooling tube surface condensation is formed is melted Discharge separates elemental sulfur and exhaust gas and reaches satisfied degree.It controls condensator outlet exhaust gas temperature and is not higher than 100 DEG C.
The molten sulfur for regenerating condenser discharge, can flow into the container of molten sulfur storage tank or haulage vehicle, since quantity is smaller, usually It is more excellent in addition to the not high purposes of individual requests such as produces sulfuric acid again containing impurity such as some organic sulfurs, phenol/quinones, cyanogen class, hydrocarbon Choosing is transported to the processing of the sulfur recovery facility with combustion furnace, is that elemental sulfur enters sulfur product by organic sulfur conversion, by phenol/quinone The burn impurities such as class, cyanogen class, hydrocarbon are removed, to convert standard compliant sulfur product for the liquid sulfur, and do not cause environment Pollution；The liquid sulfur of condenser discharge, which can also be cooled down directly, is made into blocky storage, transport.A small amount of waste water collected by condenser is gone Sour water pipeline or storage tank before stripper.
If more containing impurity such as organic sulfur, phenol/quinones, cyanogen class, the hydrocarbon for being not easy to convert in ammonia, desulfurizing and purifying Ta Yifa Raw organic sulfur, phenol/quinones, cyanogen class, hydrocarbon etc. penetrate and are not susceptible to H2When penetrating of S, it is contemplated that individually carry out such as 150 DEG C of left sides Right impurity is blown down, and at this time elemental sulfur will not be blown out substantially, but adsorbed organic sulfur, phenol/quinones, cyanogen class, hydrocarbon are most of Can deviate from, nitrogen should be passed through in desulfurizing decontaminating agent bed at this time, carbon dioxide is continuously purged, will desorption object blowout, into One step empties surface and inner hole, restores adsorption cleaning performance.
It should be pointed out that moisture content increased in ammonia in the present invention after desulfurizing and purifying, incrementss are mainly taken The certainly H in raw material ammonia2S content.
When adsorption desulfurizing agent passes through the use of long period, performance decline is unloaded to a certain extent before agent scraps, and can be carried out again Raw processing, by adsorbed elemental sulfur, organic sulfur, phenol/quinones, cyanogen class, NH3、CO2Equal gasifications are blown down, and treated, and useless agent is basic There is no peculiar smell, unloads agent process safety health, basic nonhazardous.Useless agent is free of Sulfur, is easy to answer because not having peculiar smell and murder by poisoning substantially With or storage, transport, processing, can be used for absorption of less demanding or purification purposes, can also be burnt up into boiler, containing going back for cobalt Receive metal.
In the desulfurizing and purifying technique of sour water stripping ammonia of the present invention, the amount of be incorporated oxygen, less slightly in purification process In and H2When amount needed for S generates simple substance reaction of Salmon-Saxl, ammonia can reach O after purification2The level of≤10ug/g, desulfurization precision is constant, Only the absorption desulfurizing and purifying tower regeneration period is slightly shorter；Usually control remnants O2Both desulfurization essence had been can guarantee when 100-800ug/g Degree, and the longer absorption desulfurizing and purifying tower regeneration period can be obtained.
In the desulfurizing and purifying technique of sour water stripping ammonia of the present invention, H contained in ammonia2S、SO2、COS、CS2It can base It is converted to elemental sulfur on this, elemental sulfur blowout and is collected through condenser, discharge when hot recycling；The conversion of end contained in ammonia is organic Sulphur, phenol/quinones, cyanogen class, hydrocarbon, absorption retention removes in absorption desulfurizing and purifying tower, is blown out during hot recycling, except small part passes through Regeneration condenser enters the elemental sulfur of condensation, remaining is mostly as exhaust gas component through stripper overhead richness H2S gas pipeline, desulfuration The processing of sulphur recyclable device combustion furnace, or remove torch burning and exhausting.
The desulfurizing and purifying technique of sour water stripping ammonia of the present invention is relatively simple, can be unattended in normal operation, far Journey monitoring control, because having the collection of liquid sulfur, storage and transportation problem and for heat problem when regeneration, need personnel on site's operation and Control.
The desulfurizing and purifying technique of sour water stripping ammonia of the invention, has the advantage that
1, ammonia sulfur content is low after purifying, and is substantially free of the impurity such as organic sulphur, phenol/quinones, cyanogen class, hydrocarbon, processes to postorder The corrosion of equipment such as compressor mitigates；
2, ammonia after purifying, impurity level can achieve H2S≤3ug/g, SO2≤ 3ug/g, organic sulfur≤3ug/g；It can be into One step prepares liquefied ammonia, is easy to reach the requirement of Liquid Anhydrous Ammonia GB536-88 Grade A standard, and colorless and transparent；
3, end contained in ammonia converts organic sulfur, phenol/quinones, cyanogen class, hydrocarbon, retains through adsorbing in absorption desulfurizing and purifying tower It after removing, is blown out during hot recycling, mostly as exhaust gas component through stripper overhead richness H2S gas pipeline, goes sulphur recovery The processing of device combustion furnace, or torch burning and exhausting is removed, solve the problems, such as puzzlement this class device；
4, purification process is reliable and stable, easy to control, and treating capacity is big, runs well unattended；
5, the whereabouts such as impure molten sulfur, regeneration tail gas are reasonable, and no waste gas and waste liquid discharge or even three-waste free discharge, no environment are dirty Dye, site environment are preferable；
6, be easy to draw off when desulfurizing decontaminating agent is scrapped, unload agent process safety health, give up agent substantially without peculiar smell, it is substantially nontoxic Evil, is easy to apply or store, transport, handle.
This purification process is adaptable, can be used for handling containing a small amount of SO2, COS, organic sulfur such as mercaptan, thioether, CS2And contain Organic sulfur, phenol/quinones, cyanogen class, hydrocarbon sour water strip ammonia, purification effect is ideal；The sour water includes oil plant, coal Sour water and partial hydrogenation caused by chemical plant, coking of coal factory, natural gas from coal factory and portion of natural gas processing unit (plant) The aqueous solution of device recycle hydrogen processing gained sulfide hydrogen and ammonia.
Detailed description of the invention
Fig. 1, ammonia desulfurizing and purifying process flow diagram.
Fig. 2, ammonia desulfurizing and purifying process flow diagram when absorption desulfurizing and purifying tower regenerates.
Fig. 3, the radial flow desulfurizing and purifying tower schematic diagram with vertical pipes heat exchange structure.
Fig. 4, the downflow system desulfurizing and purifying tower schematic diagram with vertical pipes heat exchange structure.
Legend: 1 desulfurizing and purifying tower shell, 2 desulfurizing decontaminating agent beds, 3 desulfurizing decontaminating agents filling pipe, 4 intake chambers, 5 heat exchange Casing inner tube, 6 heat exchange sleeve outer tubes, 7 partitions, radial reaction bed container of 8 side walls with venthole, 9 radial directions with venthole Reaction bed inner tube, 10 vertical water cooling heat exchange sleeves, 11 support porcelain balls, 12 discharge outlet, 13 water inlets, 14 desulfurizing decontaminating agents unload agent Mouthful, 15 ammonia imports or outlet, 21 drip chambers, 22 cooling/condensers.
Specific embodiment
Embodiment
A set of ammonia desulfurization purifier, process flow such as attached drawing 1 are established in coal plant sour water stripper plant It is shown.
Ammonia desulfurization purifier mainly includes sequentially connected H along airflow direction2S concentration in-line analyzer, oxygen are matched Enter pipe and static mixer, two 20M can be series-parallel and can cut out3Downflow system desulfurization with vertical pipes heat exchange structure is net Change tower；One 1M of desulfurizing and purifying tower bottom outlet connection3Simple substance sulfur condenser (water cooling, heat exchange area 15M2), the condenser is available Make to condense elemental sulfur when ammonia cooling or regeneration；Wherein the overall structure of desulfurizing and purifying tower is as shown in Fig. 4, under ammonia is enterprising Out.
In ammonia desulfurization purifier, desulfurizing and purifying tower includes reactor body, water vapor heat-tranferring system, reactor body It is not connected to water vapor heat-tranferring system；Reactor body includes shell 1, reactive desulfurizing agent bed 2, ammonia inlet and outlet 15, desulfurization Agent filling pipe 3, desulfurizing agent unload agent mouth 14；Desulfurizing agent bed bottom is supported by porcelain ball 11；Water vapor heat-tranferring system includes intake chamber 4, drip chamber 21, vertical water cooling move thermal sleeve 10, move thermal sleeve and are formed by inner tube 5 is nested with outer tube 6, outer tube upward opening is in row Water chamber bottom plate extends downwardly under desulfurizing agent bed position and in lower end closure；Inner tube lower end extends to outer pipe bottom, upper end It extends to except outer tube upper port；The height 4.5m of desulfurizing agent bed；Move the spacing 56mm, casing inner tube Φ of thermal sleeve 19x2mm, outer tube Φ 38x3mm, casing radical 680,360 m of heat exchange area3；Reactor diameter Φ 2600mm, total high 7500mm.
Load 10M in desulfurizing and purifying tower middle and upper part39M is loaded in XDS-2 ammonia desulfurizing agent, lower part3XDS-1 ammonia desulfurizing agent, bottom Load 0.6M in portion3Inert ceramic balls support.Two kinds of ammonia desulfurizing agents of described XDS-2, XDS-1 are that Shandong is fast limited up to Chemical Group The product grade of company is all activated carbon modified Fine Desulfurizer at Ambient Temperature, mainly by by H2S and O2Reaction generates elemental sulfur simultaneously Absorption deposits and removes H contained by ammonia2S, in H2S 0-2%(volume) wider range in, with slightly more O2And it mixes well When can handle to H2S≤3ug/g, working sulfur capacity >=20% (quality), wherein XDS-1 ammonia desulfurizing agent also has certain organic Sulphur hydrolysis ability, can be by COS, CS2It is hydrolyzed to H2S simultaneously further generates elemental sulfur adsorbing and removing；Both ammonia desulfurizing agents Can also adsorbing and removing end conversion organic sulfur and phenol/quinones, cyanogen class, hydrocarbon, removing precision can be usually reached organic matter≤3ug/g It is horizontal；In 40-50 DEG C or so of temperature condition, two kinds of desulfurizing agents in above-mentioned filling ratio, tempreture organic sulphur hydrolysis conversion with Residual organic sulfur, phenol/quinones, cyanogen class, the overall performance of hydrocarbon absorption are preferable.Two kinds of ammonia desulfurizing agents of described XDS-2, XDS-1, also It can be purged by 250-300 DEG C of hot recycling and indifferent gas, blow down the elemental sulfur, organic sulfur and phenol/quinones, cyanogen for adsorbing deposition The ingredients such as class, hydrocarbon restore its desulfurizing and purifying performance substantially.
The main operating process conditions of ammonia desulfurization purifier are as follows:
Strip basic composition (volume content) and the flow of ammonia: H2S0.8-1.0%, COS0.005-0.01%, CS20.01-0.03%, H2O 1.0-1.5%, containing other organic sulfurs, phenol/quinones, cyanogen class, hydrocarbon 300-600ppm, remaining is ammonia, Flow 300-400NM3/h；According to H2The amount of S is incorporated oxygen to O2Excessive about 0.02%；
33 DEG C of the ammonia inlet temperature of desulfurizing and purifying tower, 33 DEG C of room temperature of water inlet, 41 DEG C of room temperature of draining, desulfurizing decontaminating agent 46 DEG C of bed temperature, 3 DEG C of the temperature difference of different height and diameter key position；It works off one's feeling vent one's spleen and forms permissible value H2S≤3ug/g NH3, SO2≤1ug/g NH3, O250-200 ug/g NH3, organic sulfur≤3 ug/g NH3, phenol/quinones+cyanogen class+hydrocarbon≤10 ug/g NH3。
After ammonia desulfurization purifier comes into operation, desulfurizing and purifying tower single-tower operation, another tower is spare, has operated 25 for the first time It, until H2S is close to the permissible value upper limit, and during which organic sulfur, phenol/quinones, cyanogen class, hydrocarbon are qualified.After cutting stand-by still, cut out with rear tower Regeneration.Before the regeneration of desulfurizing and purifying tower, the acidity before the ammonia in desulfurizing and purifying tower to be first purged to nitrogen stripper entrance is dirty It is absorbed in water, a small amount of air is incorporated before being passed through sour water prevents sour water from quickly inhaling ammonia refluence into desulfurizing and purifying Tower；The water of intake chamber, drip chamber is blown out as far as possible with purification wind, is collected into water pot.
During the hot recycling of desulfurizing and purifying tower, circulation heating, hot wind are beaten with the 280-350 DEG C of hot wind preheated in heating furnace It flows down from intake chamber into casing inner tube, then from outer pipe bottom upstream returning drainage room, 350 DEG C of hot blast temperature when regeneration starts, with bed The rising of layer temperature is gradually decreased to 300 DEG C, 280 DEG C of hot blast temperature when constant temperature；Nitrogen progress is passed through into desulfurizing decontaminating agent bed Continuous purging, into condenser, initial stage condensation waste water removes Water Tank before stripper for reactivation outlet material, gas, melts, the list of gasification blowout The condensation of matter sulphur and collection, contain organic sulfur, phenols, cyanogen class, hydrocarbon, NH3、CO2Exhaust gas through condenser exhaust gas mouth connect stripper overhead richness H2S gas pipeline, goes combustion furnace of sulfur recovery device to handle.It is regenerated to after working off one's feeling vent one's spleen 250 DEG C of temperature, stops Hot-blast Heating, continue After nitrogen purge 10 hours, desulfurizing and purifying tower intake chamber, drip chamber use cooling cooling water circulation instead to stopping nitrogen after 50 DEG C, Switchback carries out ammonia desulfurizing and purifying, and another tower cuts out spare.It is continued to use after the drained molten sulfur of condenser as ammonia cooler.Heat is again The raw molten sulfur for collecting discharge is condensed into bulk, and gross weight 2800kg illustrates desulfurization capacity of the desulfurizing agent under above-mentioned use condition extremely It is less 20%(mass).
After desulfurizing and purifying tower completion first time hot recycling comes into operation, it have passed through 10 regeneration periods, each regenerated operating Time is all H at 25 days or so2S is close to the permissible value upper limit, and during which organic sulfur, phenol/quinones, cyanogen class, hydrocarbon are all qualified, place The liquefied ammonia of ammonia further processing production after reason, total S≤1ug/g is colorless and transparent, reaches Liquid Anhydrous Ammonia GB536-88 Grade A The requirement of standard illustrates XDS-2, XDS-1 desulfurizing agent using effect in ammonia desulfurization purifier operation process of the invention Preferably, its performance is restored substantially after hot recycling, also illustrates ammonia desulfurization purifier of the invention to H2S, organic sulfur, phenols, Cyanogen class, the removing clean-up effect of hydrocarbon are preferable.
Ammonia desulfurization purifier of the invention, the quality of technology controlling and process and obtained ammonia, liquefied ammonia are all substantially better than The NH used before4HS crystallization+old the technique of desulfurizing agent, the NH of old technique4HS crystalline quality is general, to organic sulfur, phenols, cyanogen class, The processing of hydrocarbon and its whereabouts arrange not reasonable.

Claims (6)

1. a kind of desulfurizing and purifying technique of sour water stripping ammonia, along ammonia flow to capital equipment include two can be series-parallel Catalysis oxidation adsorbs desulfurizing and purifying tower, and the heat exchanger tube of mild heat desulfurizing agent bed can sufficiently drop in setting in desulfurizing and purifying tower, Desulfurizing and purifying tower lower part outlet connection regeneration condenser, regeneration condenser bottom have liquid elemental sulfur can accomplished continuously or intermittently be discharged But the sulfur outlet of gas is not discharged；
Ammonia is incorporated oxygen and is mixed well before entering absorption desulfurizing and purifying tower, the amount of allocating of oxygen is slightly more than anti-with sulfide O needed for elemental sulfur should be generated2Amount, the sulfide concentration on-line determination in ammonia；
Adsorb desulfurizing and purifying tower filling can hot recycling catalytic oxidation adsorption desulfurizer, 10-60 DEG C of operation temperature, will be contained by ammonia A small amount of organic sulfur, phenol/quinones, cyanogen class, hydro carbons absorption, by contained minute quantity SO2With contained H2S reaction is converted into elemental sulfur and inhales It is attached, by remaining H2S is oxidized to elemental sulfur and is adsorbed in inner hole between particle；H in ammonia after processing2S≤3ug/g, SO2≤ 3ug/g, organic sulfur≤3ug/g are substantially free of phenol/quinones, cyanogen class, hydro carbons；
It is more than desulfurization after specified value that desulfurizing and purifying tower, which operates sulfide, phenol/quinones, cyanogen class, one of hydro carbons into outlet ammonia, Purifying column cuts out elemental sulfur, the sulfide, phenol/quinones, cyanogen class, hydro carbons for carrying out hot recycling blowing absorption deposition；It is arranged when hot recycling Material, gas out enters regeneration condenser, and wherein molten sulfur and sulfur vapor are condensed into liquid sulfur, solid-state sulfur recovery, containing organic sulfur, phenol/ Quinones, cyanogen class, hydrocarbon, NH3、CO2Exhaust gas be incorporated to stripper overhead richness H2S gas pipeline, goes combustion furnace of sulfur recovery device to handle, Or burn-up is gone to empty into flare line；
Vertical pipes heat exchange structure is used in the desulfurizing and purifying tower；
The desulfurizing and purifying tower with vertical pipes heat exchange structure, the cooling water for using temperature slightly lower as move thermal medium, water inlet, Draining and its distribution into casing, from collecting in casing, be all disposed within intake chamber, the drip chamber of desulfurizing and purifying top of tower； Casing extends down into desulfurizing decontaminating agent bed, until the bottom of desulfurizing decontaminating agent bed；The vertical pipes by inner tube and Outer tube nesting forms, and inner tube, the upper port of outer tube are separately connected intake chamber, drip chamber, end closure under outer tube, and inner tube lower end extends To outer tube lower end and be open, inner tube water to flow down, outer tube water Xiang Shangliu, inner tube, outer tube water, carbonated drink flow direction, pass through cooling water Circulation pump power is formed；
250-300 DEG C of the hot regeneration temperature of desulfurizing and purifying tower, and nitrogen, carbon dioxide progress are passed through into desulfurizing decontaminating agent bed Continuous purging；During hot recycling, 250-350 DEG C of hot wind, steam or conduction oil are passed through as heat medium to intake chamber；Add Thermal medium from top to bottom, then from outer tube from bottom to top returns to drip chamber from the inner tube of casing；Intake chamber, draining after the completion of hot recycling Lead to cooling water in room, casing heat-tranferring system to be down to 40 DEG C or less for use or come into operation.
2. the desulfurizing and purifying technique of sour water stripping ammonia as described in claim 1, which is characterized in that catalysis oxidation absorption There is desulfurizing agent tempreture organic sulphur hydrolysis to convert removing ability, and can restore substantially its performance by hot recycling.
3. the desulfurizing and purifying technique of sour water stripping ammonia as described in claim 1, which is characterized in that the vertical water cooling Casing gos deep into the height 0.5-10m of desulfurizing decontaminating agent bed, tube spacing 0.05-0.10m, heat exchange area 5-30m2/m3Desulfurizing and purifying Agent.
4. the desulfurizing and purifying technique of sour water stripping ammonia as described in claim 1, which is characterized in that desulfurizing decontaminating agent bed The structure of layer is axially or radially according to ammonia flow direction.
5. the desulfurizing and purifying technique of sour water stripping ammonia as claimed in claim 4, which is characterized in that desulfurizing decontaminating agent bed Layer is the axial arrangement of ammonia upper entering and lower leaving.
6. the desulfurizing and purifying technique of sour water stripping ammonia as described in claim 1, which is characterized in that desulfurizing decontaminating agent bed Filling inert ceramic balls are as support under layer.
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