CN107737520A - The method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated - Google Patents

The method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated Download PDF

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Publication number
CN107737520A
CN107737520A CN201710966851.5A CN201710966851A CN107737520A CN 107737520 A CN107737520 A CN 107737520A CN 201710966851 A CN201710966851 A CN 201710966851A CN 107737520 A CN107737520 A CN 107737520A
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flue gas
reactor
absorbing liquid
nitrogen
sodium alkali
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CN201710966851.5A
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Inventor
瞿赞
晏乃强
贾金平
谢江坤
方丽
陈丽红
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/76Gas phase processes, e.g. by using aerosols
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 absorption
    • B01D53/1425Regeneration of liquid absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 absorption
    • B01D53/1456Removing acid components
    • B01D53/1481Removing sulfur dioxide or sulfur trioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/14Separation 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 absorption
    • B01D53/1493Selection of liquid materials for use as absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/54Nitrogen compounds
    • B01D53/56Nitrogen oxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/69Sulfur trioxide; Sulfuric acid
    • C01B17/74Preparation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/10Oxidants
    • B01D2251/104Ozone
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10Inorganic absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/50Combinations of absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/025Other waste gases from metallurgy plants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/10Capture or disposal of greenhouse gases of nitrous oxide (N2O)
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/151Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

The present invention relates to a kind of method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated, by adding ozone into flue gas, NO is converted into NO2, afterwards using sodium sulfite in flue gas and the NO that deposits2、SO2Synchronize absorption; then the reduction denitrification of absorbing liquid Nitrite and nitrate anion is strengthened by electrochemical method; and the sodium hydrogensulfite of generation is regenerated using steam heating and nitrogen protection, while recyclable high concentration SO is concentrated to give by nitrogen extracting2, finally realize depth denitration and the SO of flue gas during smelting2Removal and Resource recovery.Compared with prior art, by this method both can synchronous depth remove NOx and SO in flue gas2, again can be by the SO of low concentration2Enrichment method, it is easy to recycle, significantly reduces the cost of chemical absorbing desulphurization denitration, be with a wide range of applications.The present invention is applied to the desulphurization denitration processing of non-ferrous metal metallurgy flue gas etc..

Description

The method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated
Technical field
The invention belongs to environmentally friendly fume treatment field, is utilized more particularly, to one kind and circulates sodium alkali to Flue Gas of Nonferrous Smelting The method for carrying out coordinated desulfurization denitration, at the flue gas desulfurization and denitrification equipped with the non-ferrous metal metallurgy enterprise of acid-making process Reason.
Background technology
China is nonferrous production big country, and ten kinds of conventional non-ferrous metal yield have occupied the world continuous more than ten year One.The tremendous development of non-ferrous metal metallurgy had both promoted the growth of economy, while also brought the environmental problem being on the rise, especially It is most representative with sulfur dioxide, the gas pollutant such as nitrogen oxides discharged in smelting process.In order to reduce non-ferrous metal The adverse effect to atmospheric environment is smelted, China has promulgated special discharge limit again on the basis of existing flue gas during smelting discharge standard The standard of value, the discharge to sulfur dioxide, nitrogen oxides etc. propose higher requirement.
In terms of flue gas desulfurization, non-ferrous metal metallurgy industry SO 2 from fume control technology is general according to its concentration level It is divided into two major classes:For high concentration SO2Flue gas, sulfuric acid is reclaimed using the double-absorption acid-making process of maturation.For middle low concentration SO2Flue gas, then handled using Wet Flue Gas Desulfurization Techniques such as sodium alkali, ammonia process, ionic liquid methods.And this kind of method is often present Efficiency is relatively low, cost is high, easily causes the deficiencies of secondary pollution.In terms of denitrating flue gas, in coal-fired flue gas denitration frequently with choosing Selecting property catalytic reduction method (SCR) technology is difficult to overcome higher concentration SO in Flue Gas of Nonferrous Smelting2And SO3Interference, and selectivity it is non- The denitration efficiency of catalytic reduction method (SNCR) technology is insufficient for the requirement of flue gas qualified discharge again.At present, in non-ferrous metal In terms of flue gas during smelting denitration, the report that correlation technique is used widely yet there are no.Therefore, existing non-ferrous metal metallurgy industry Flue gases purification can not realize the efficient removal to sulfur and nitrogen oxides, more lack the collaboration of sulphur/nitre synchronization emission reduction Control technology.It is necessary that seeking new technique or group technology solves the problems, such as sulphur/nitre synchronization emission reduction of non-ferrous metal metallurgy flue gas.
The content of the invention
Soda is circulated it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind utilizes The method that method carries out coordinated desulfurization denitration to Flue Gas of Nonferrous Smelting.
The purpose of the present invention can be achieved through the following technical solutions:One kind utilizes and circulates sodium alkali to nonferrous smelting cigarette The method that gas carries out coordinated desulfurization denitration, it is characterised in that including following steps:
The first step, the flue gas during smelting after dedusting, cooling processing is passed through in oxidation reactor (2);
Second step, ozone is produced by ozone generator (1) and is passed through in oxidation reactor (2), by ozone by flue gas NO be oxidized to NO2
3rd step, the flue gas after oxidation reaction is passed through in sulphur/nitre absorption tower (3), using main absorbent and strengthens absorption Agent is to the SO in flue gas2, NO and NO2Absorption, cleaning flue gases discharge are synchronized, liquid is inputted in absorbing liquid circulating slot (4)
4th step, the part solution in absorbing liquid circulating slot (4) is injected into electrochemical reduction denitrification reactor (5), utilized Nitrite anions in absorbing liquid, nitrate anion are carried out reduction denitrogenation processing by electrochemical method, are translated into N2Directly discharge;
5th step, the part solution in absorbing liquid circulating slot (4) is injected into desulfurization regeneration device (6), utilizes high temperature nitrogen Absorbing liquid is heated, by the NaHSO in solution3It is converted into Na2SO3With high concentration SO2, wherein Na2SO3Absorbing liquid is injected back into follow Continue to absorb the SO in flue gas in annular groove (4)2And NO2, and the high concentration SO concentrated2Then it is input to acid plant and prepares sulfuric acid.
Described flue gas during smelting had carried out high-effective dust-removing and cooling processing, between its flue-gas temperature is 120-200 DEG C Temperature section.
It is 0.5-1.2 that unit interval, which sprays into the ozone of oxidation reactor (2) and the molar ratio range of nitrogen oxides in effluent,.
Described main absorber is Na2SO3, described reinforcing absorbent is vulcanized sodium.
For described electrochemical reduction denitrification reactor (5) using electrochemical reactor, electrochemical reactor is pole plate Reactor or three-dimensional reactor.
5th step is that absorbing liquid is regenerated, and is that the absorbing liquid in desulfurization regeneration device (6) is entered using the nitrogen of heat Row processing, nitrogen temperature are 95-100 DEG C.
Described high concentration SO2Refer to the gas that nitrogen is discharged to desulfurization regeneration device (6) after nitrogen regeneration, by it As feedstock transportation to acid plant, SO2Concentration is in the range of 10-20%.
The present invention proposes a kind of method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated.Tool Body is by adding ozone into flue gas, and NO is converted into NO2, afterwards using sodium sulfite in flue gas and the NO that deposits2、SO2Enter The synchronous reduction denitrification and heating for absorbing, then strengthening absorbing liquid Nitrite and nitrate anion by electrochemical method of row Nitrogen is to SO2Extracting, regeneration and inspissation, finally realize depth denitration and the SO of flue gas during smelting2Removal and Resource recovery Change.
Compared with prior art, the present invention has advantages below:
1st, the group technology that the present invention is absorbed using ozone oxidation and sodium sulfite, can be directed to non-ferrous metal metallurgy flue gas The sulfur dioxide and nitrogen oxides of middle low concentration synchronize absorption processing, realize the collaboration emission reduction of pollutant;
2nd, the electrochemical method that the present invention uses can carry out nitrite anions/nitrate anion in absorbing liquid to reduce at denitrogenation Reason, realizes the deep removal of nitrogen oxides in effluent, and do not have secondary pollution;
3rd, the renovation process that the present invention uses can extract the sulfur dioxide concentration in absorbing liquid, and for preparing Sulfuric acid, realize the recycling of sulfur dioxide;
4th, the present invention be applied to non-ferrous metal metallurgy flue gas it is special when exhaust gas volumn is small, flue-gas temperature is low and oxysulfide and The relatively low flue gas desulfurization and denitrification processing of nitrous oxides concentration.
Brief description of the drawings
Fig. 1 is the schematic diagram that the present invention uses technique.
Embodiment
The present invention is further described with reference to specific embodiment.The present embodiment is before with technical solution of the present invention Put and implemented, give detailed embodiment and specific operation process, but protection scope of the present invention be not limited to it is following Embodiment.
Embodiment 1
The present embodiment chooses a homemade revolving burner as flue gas occurrence of equipment, former for mixing with lead concentrate powder and fire coal Material carries out calcination process, there is provided the Flue Gas of Nonferrous Smelting of workshop section is smelted close to actual lead.Exhaust gas volumn is about 200m3/ h, in flue gas NO、SO2Concentration be respectively 200mg/m3And 2000mg/m3.Rotation outlet of still tail gas is passed through into an electrostatic precipitator and air After heat exchanger, a flue gas oxidation unit is introduced, ozone is prepared using an ozone generator (60g/h) and is passed through flue gas oxygen During makeup is put, the NO in flue gas is oxidized to NO using ozone2, wherein O3/ NO mol ratio is about 0.9:1.By ozone oxidation Flue gas afterwards is introduced into smoke absorption tower, with Na2SO3It is absorbing liquid to the NO in flue gas2、SO2Absorbed.Absorbing liquid with The liquid-gas ratio for handling flue gas is 5L/m3.Flue gas after to absorption tower is monitored, as a result indicate processing after flue gas NO, SO2Concentration is respectively:30mg/m3And 100mg/m3, denitrating flue gas and desulfuration efficiency are respectively 85% and 95%.
Embodiment 2
The present embodiment equally chooses the experimental study that above-mentioned experimental system carries out sulphur/nitre collaboration emission reduction.This exhaust gas volumn flue gas Amount is about 200m3/ h, NO, SO in flue gas2Concentration be respectively 200mg/m3And 2000mg/m3.Using ozone by the NO in flue gas It is oxidized to NO2, wherein O3/ NO mol ratio is about 1.1:1.Flue gas after ozone oxidation is introduced into smoke absorption tower, with Na2SO3It is absorbing liquid to the NO in flue gas2、SO2Absorbed.Absorbing liquid and the liquid-gas ratio of processing flue gas are 5L/m3.By pair Flue gas behind absorption tower is monitored, and as a result indicates flue gas NO, SO after processing2Concentration is respectively:10mg/m3And 100mg/m3, Denitrating flue gas and desulfuration efficiency are respectively 95% and 95%.
Embodiment 3
As shown in figure 1, a kind of method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated, including Following steps:
The first step, the flue gas during smelting that the temperature after dedusting, cooling processing is 120-200 DEG C is passed through oxidation reactor (2) in;
Second step, ozone is produced by ozone generator 1 and is passed through in oxidation reactor 2, the unit interval sprays into oxidation reaction The ozone of device 2 and the molar ratio range of nitrogen oxides in effluent are 0.5-1.2, and the NO in flue gas is oxidized into NO by ozone2
3rd step, the flue gas after oxidation reaction is passed through in sulphur/nitre absorption tower 3, utilizes main absorbent Na2SO3Inhaled with strengthening Agent vulcanized sodium is received to the SO in flue gas2, NO and NO2Synchronize absorption, cleaning flue gases discharge, liquid input absorbing liquid circulating slot 4 In;
4th step, the part solution in absorbing liquid circulating slot 4 is injected into the electrochemical reaction of electrochemical reduction denitrification reactor 5 Device, the nitrite anions in absorbing liquid, nitrate anion are subjected to reduction denitrogenation processing using electrochemical method, are translated into N2Directly Discharge;
5th step, the part solution in absorbing liquid circulating slot 4 is injected into desulfurization regeneration device 6, it is high using 95-100 DEG C of hair Warm nitrogen heats to absorbing liquid, by the NaHSO in solution3It is converted into Na2SO3With high concentration SO2, wherein Na2SO3It is injected back into suction Receive and continue to absorb the SO in flue gas in liquid circulating slot 42And NO2, and the high concentration SO concentrated2(concentration is in the range of 10-20%) then It is input to acid plant and prepares sulfuric acid.

Claims (7)

  1. A kind of 1. method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated, it is characterised in that including Following steps:
    The first step, the flue gas during smelting after dedusting, cooling processing is passed through in oxidation reactor (2);
    Second step, ozone is produced by ozone generator (1) and is passed through in oxidation reactor (2), by ozone by the NO in flue gas It is oxidized to NO2
    3rd step, the flue gas after oxidation reaction is passed through in sulphur/nitre absorption tower (3), using main absorbent and strengthens absorbent pair SO in flue gas2, NO and NO2Absorption, cleaning flue gases discharge are synchronized, liquid is inputted in absorbing liquid circulating slot (4)
    4th step, the part solution in absorbing liquid circulating slot (4) is injected into electrochemical reduction denitrification reactor (5), utilizes electrification Nitrite anions in absorbing liquid, nitrate anion are carried out reduction denitrogenation processing by method, are translated into N2Directly discharge;
    5th step, the part solution in absorbing liquid circulating slot (4) is injected into desulfurization regeneration device (6), using high temperature nitrogen to inhaling Receive liquid to be heated, by the NaHSO in solution3It is converted into Na2SO3With high concentration SO2, wherein Na2SO3It is injected back into absorbing liquid circulating slot (4) continue to absorb the SO in flue gas in2And NO2, and the high concentration SO concentrated2Then it is input to acid plant and prepares sulfuric acid.
  2. 2. it is according to claim 1 it is a kind of using circulate sodium alkali to Flue Gas of Nonferrous Smelting carry out coordinated desulfurization denitration side Method, it is characterised in that described flue gas during smelting had carried out high-effective dust-removing and cooling processing, and its flue-gas temperature is 120-200 Temperature section between DEG C.
  3. 3. it is according to claim 1 it is a kind of using circulate sodium alkali to Flue Gas of Nonferrous Smelting carry out coordinated desulfurization denitration side Method, it is characterised in that the ozone of unit interval penetrating oxidation reactor (2) and the molar ratio range of nitrogen oxides in effluent are 0.5-1.2。
  4. 4. it is according to claim 1 it is a kind of using circulate sodium alkali to Flue Gas of Nonferrous Smelting carry out coordinated desulfurization denitration side Method, it is characterised in that described main absorber is Na2SO3, described reinforcing absorbent is vulcanized sodium.
  5. 5. it is according to claim 1 it is a kind of using circulate sodium alkali to Flue Gas of Nonferrous Smelting carry out coordinated desulfurization denitration side Method, it is characterised in that described electrochemical reduction denitrification reactor (5) is using electrochemical reactor, electrochemical reactor For pole plate reactor or three-dimensional reactor.
  6. 6. it is according to claim 1 it is a kind of using circulate sodium alkali to Flue Gas of Nonferrous Smelting carry out coordinated desulfurization denitration side Method, it is characterised in that the 5th step is regenerated to absorbing liquid, is to the suction in desulfurization regeneration device (6) using hot nitrogen Receive liquid to be handled, nitrogen temperature is 95-100 DEG C.
  7. 7. it is according to claim 1 it is a kind of using circulate sodium alkali to Flue Gas of Nonferrous Smelting carry out coordinated desulfurization denitration side Method, it is characterised in that described high concentration SO2Refer to the gas that nitrogen is discharged to desulfurization regeneration device (6) after nitrogen regeneration Body, as feedstock transportation to acid plant, SO2Concentration is in the range of 10-20%.
CN201710966851.5A 2017-10-17 2017-10-17 The method that coordinated desulfurization denitration is carried out to Flue Gas of Nonferrous Smelting using sodium alkali is circulated Pending CN107737520A (en)

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CN109092017A (en) * 2018-09-19 2018-12-28 上海交通大学 A kind of method that flue gas oxidation and denitration controls nitrate generation in absorbing liquid
CN112915755A (en) * 2021-02-08 2021-06-08 上海交通大学 System and method for jointly recovering sulfur dioxide in flue gas and removing nitrogen oxide
CN112933966A (en) * 2021-02-28 2021-06-11 中国海洋大学 Photocatalytic oxidation desulfurization and reduction denitration process for ship flue gas

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CN109092017A (en) * 2018-09-19 2018-12-28 上海交通大学 A kind of method that flue gas oxidation and denitration controls nitrate generation in absorbing liquid
CN112915755A (en) * 2021-02-08 2021-06-08 上海交通大学 System and method for jointly recovering sulfur dioxide in flue gas and removing nitrogen oxide
CN112933966A (en) * 2021-02-28 2021-06-11 中国海洋大学 Photocatalytic oxidation desulfurization and reduction denitration process for ship flue gas

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Application publication date: 20180227