CN107261664A - 一种合成革工艺中废气和废液的联合处理工艺 - Google Patents
一种合成革工艺中废气和废液的联合处理工艺 Download PDFInfo
- Publication number
- CN107261664A CN107261664A CN201710701516.2A CN201710701516A CN107261664A CN 107261664 A CN107261664 A CN 107261664A CN 201710701516 A CN201710701516 A CN 201710701516A CN 107261664 A CN107261664 A CN 107261664A
- Authority
- CN
- China
- Prior art keywords
- waste gas
- waste
- gas
- dimethylamine
- rco
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002912 waste gas Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 58
- 230000008569 process Effects 0.000 title claims abstract description 27
- 239000002649 leather substitute Substances 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000011282 treatment Methods 0.000 title claims abstract description 17
- 239000002699 waste material Substances 0.000 title claims abstract description 17
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 27
- 238000010521 absorption reaction Methods 0.000 claims abstract description 17
- 239000006096 absorbing agent Substances 0.000 claims abstract description 16
- 238000002485 combustion reaction Methods 0.000 claims abstract description 16
- 238000003795 desorption Methods 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims description 27
- 239000012855 volatile organic compound Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000003546 flue gas Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 6
- 238000009825 accumulation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003344 environmental pollutant Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 239000010815 organic waste Substances 0.000 claims description 5
- 231100000719 pollutant Toxicity 0.000 claims description 5
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000004146 energy storage Methods 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000007791 liquid phase Substances 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000010908 plant waste Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000002041 carbon nanotube Substances 0.000 description 9
- 229910021393 carbon nanotube Inorganic materials 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000007689 inspection Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000010985 leather Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 150000001206 Neodymium Chemical class 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000011953 bioanalysis Methods 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001066 destructive effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical class [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VNFVKWMKVDOSKT-LREBCSMRSA-N (2r,3r)-2,3-dihydroxybutanedioic acid;piperazine Chemical compound C1CNCCN1.OC(=O)[C@H](O)[C@@H](O)C(O)=O VNFVKWMKVDOSKT-LREBCSMRSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
-
- 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
- B01D53/06—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 moving adsorbents, e.g. rotating beds
-
- 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
- B01D53/26—Drying gases or vapours
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- 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
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/116—Molecular sieves other than zeolites
-
- 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
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
-
- 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
- B01D2259/40088—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating
- B01D2259/4009—Regeneration of adsorbents in processes other than pressure or temperature swing adsorption by heating using hot gas
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/38—Polymers
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biomedical Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
本发明提供一种合成革工艺中废气和废液的联合处理工艺,该工艺将合成革生产干法、湿法和后处理车间废气通过转轮吸附器吸附,将吸附后准备排放的气体用作二甲胺废水的吹脱气,二甲胺废水经吹脱塔得到废气与来自转轮吸附器脱附区浓缩的废气一起进入RCO炉催化燃烧,由于催化剂的SCR催化效果,燃烧烟气中NOx浓度得到控制。
Description
技术领域
本发明涉及环保技术领域,特别涉及一种合成革工艺中废气和废液的联合处理工艺。
背景技术
PU合成革生产过程中需大量使用有机原料,废气产生量大,且我国合成革企业治理措施普遍落后,VOCs污染严重。某合成革企业主要生产鞋革、箱包革、服装革等油性PU合成革产品,具有干法生产线3条,湿法生产线4条,揉纹机、印刷机等后处理设备若干,在生产过程中会产生大量含烷烃、芳香烃、酮类、二甲胺等VOCs的有机废气。目前主要利用普通的级喷淋塔"对工艺废气中的DMF进行回收,有些企业也使用低温等离子体设备,对后处理车间的工艺废气进行处理,但总VOCs去除率过低,难以满足要求。同时企业对预含浸槽废液和喷淋塔吸附区中的DMF进行精傭处理,会产生大量含二甲胺的塔顶废水,企业将其喷入锅炉燃烧,导致锅炉烟气中NO、严重超标。
VOCs处理技术可分为两类:一类为非破坏性技术,如吸附法、冷凝法等;另一类为破坏性处理技术,如生物法、等离子体法、燃烧法等。其中吸附法一般作为巧缩预处理工艺使用,若直接对饱和的吸附区进行拋弃更换,经济性差,且会形成难以处理的危废;冷凝法能耗较高,一般只适用于高沸点和高巧度VOCs的回收生物法在使用中受到VOCs组分的限制,对有机硫化物、苯系化合物等有机物降解困难,且微生物培养耗时较长,对运行条件要求严格。目前实际应用较多的VOCs废气处理技术为低温等离子体法和燃烧法(含热力焚烧、催化燃烧等)。
等离子体法是利用高能电子射线激活、电离、裂解VOCs中各组分,促发氧化等一系列化学反应,达到降解VOCs的效果。该技术的处理量大,能耗低,适用范围广,但在存在对VOCs降解不完全的缺点,反应过程中会产生大量副产物。
本发明的目的就在于克服上述缺点和不足,针对合成革行业的典型污染设计出可行、高效的废气治理工艺实现Cl-VOCs的低成本的处理工艺,恢复合成革企业聚集地的环境空气质量。
发明内容
本发明提供一种合成革工艺中废气和废液的联合处理工艺,包括以下步骤:
废气首先经吸附过滤器去除固体颗粒和油性雾滴,经预过滤处理的有机废气分两股进入转轮吸附器,部分直接废气进入转轮吸附器,经分子筛吸附VOCs污染物吸附效率>90%,然后由风机导入二甲胺废液吹脱塔;其余废气通过转轮冷却区,再进入管式换热器,升温后进入转轮脱附区,由高温废气脱附再生,所产生高浓度废气与来自二甲胺吹脱塔中的废气一起导入干燥塔中,干燥后转入进入RCO反应器中,在入口蓄热窒内吸热升温后,与催化剂床层接触进行催化燃烧反应,实现VOCs降解,该过程伴随着SCR反应(二甲胺对NOx还原)的进行,烟气中NOx含量得到了有效控制。同时从RCO反应器的燃烧室上端抽取少量烟气,通过管式换热器对脱附废气加热。烟气流经出口蓄热室,传热后自身温度降低,由双向切换阀排出RCO反应器,通过排气筒高空排放。双向切换阀在PLC系统控制下毎2分钟切换一次,废气流向随之改变,如此循环反复从两侧进出RCO反应器,充分回收利用燃烧烟气热量。
由于吸收过程是一个放热过程,加之废气本身的温度较高(50-60℃)以及外环境(阳光照射)都会增加转轮吸附器内吸附区的温度,导致吸附区的温度随着系统运转时间的延长而逐渐升高。因而本发明优选地,在转轮吸附器前设置有冷却装置,在处理废气的同时不断对吸附区进行降温冷却,保证吸附区的温度稳定。
吹脱塔是吹脱工序的主要设备,利用二甲胺沸点低、水解呈碱性的特点,通过升温和加碱,促进二甲胺分子在填料表面由液相向气相转移,使二甲胺废水吹脫形成二甲胺废气进入后续工艺处理。
废气燃烧处理前,应先对RCO炉进行预热吹扫,使蓄热床屋升温至350℃,吹扫空气风量取2000Nm3/h,25℃,燃烧机功率为12~60W,散热取5%。
吸附过滤器前后端、转轮吸附段前后端、RCO炉废气进出口均安装有压差变送器,信号输出至PLC中控系统。当吸附过滤器前后端压差达到1000Pa保持10s以上时,系统发出警报并关闭主风机、脱附风机,需更换吸附过滤器巧的过滤棉;当转轮吸附段前后端的压降达到800pa并保10s以上时,系统发出警报并自动关闭主风机和脫附风机,需进行停机检查;当RCO炉废气进出口的压降达到4kPa并保持10s以上时,系统发出警报并自动关闭脱附风机、吹脱风机和烟气风机,需进行停机检查。
转轮脱附段进气口、RCO炉催化剂床层上部和RCO炉蓄热体床层底部均有热电偶,信号输出至PLC中控系统。系统根据热电偶反馈信号对燃燒机和换热风机进行调节,控制脱附废气温度在200℃左右,RCO炉内温度在350℃左右。当转轮脱附段进气口废气温度达到250℃时并保持10s以上时,系统发出警报并关闭脱附风机、换热风化,需进行停机检查;当RCO炉催化剂床层上部温度达到450℃并保持10s以上时,系统发出警报并关闭燃烧机、吹脱风机和脫附风机,需进行停机检查;当RCO炉蓄热体床层底部温度达到100℃并保持10s以上时,系统发出警报并关闭燃烧机、吹脱风化和脱附风机,需进行停停机检查。
所述RCO反应器中装载有SCR催化剂,本发明所述SCR催化剂优选是以碳纳米管(CNTS)为载体,NdO2为活性组分,碱金属为助剂;其中,NdO2占催化剂重量的20-50%,碱金属占催化剂重量的0.1%~2%,余量为CNTS;所述碱金属为Li、Na、K、Ru、Cs中的一种或几种。
碳纳米管,又名巴基管,主要由呈六边形排列的碳原子构成数层到数十层的同轴圆管组成,是由日本电镜学家饭岛发现的。一经发现,便在各个领域掀起了碳纳米管的研究热潮,研究的内容包括:碳纳米管的制备、性能及应用。通过研究人们发现气相沉积法可以大规模地合成碳纳米管,使得碳纳米管的成本得到有效的降低,这也为碳纳米管的应用提供了坚实的基础。对碳纳米管性能的研究揭示:碳纳米管是碳的一种同素异形体,其孔径可以从几个纳米到100nm。由于它是由石墨演化而来,因而仍有大量未成对电子沿管壁游动,事实上,碳纳米管既具有金属的导电性,又具有半导体性能,尤其是由于某些特别的缺陷也可能导致同一碳管既具有金属的性质,又具有半导体的性质。通过在单个碳纳米管上引入缺陷,再通过调整缺陷在碳纳米管上的位置,可在很大范围内改变和调节碳纳米管的这种电性能。且碳纳米管比表面积大,硬度高,具有高热稳定性。碳纳米管的特殊性导致对其应用的广泛研究,在催化科学领域也不例外。鉴于碳纳米管的诸多特性,人们开展了将其作为催化剂载体的研究。
由于碳纳米管表面的疏水性,使得采用浸渍法把活性组分负载于碳纳米管上时,不能把活性组分溶于水性溶剂,而必须采用乙醇,苯,丙酮等有机溶剂。张爱民等有关碳纳米管的吸附实验表明:碳纳米管具有较强的吸附正己烷的能力,对乙醇的吸附较弱,但仍大大强于对水的吸附。实验结果还表明碳纳米管的提纯和开管率是影响吸附性能的重要因素。张宇在实验中也发现碳纳米管对苯有强吸附作用,表面具有强疏水性。综合考虑活性组分在溶剂中的溶解性以及溶剂在碳纳米管上的吸附性能,当催化剂的活性组分为金属有机化合物时,多使用苯或丙酮等溶剂;当催化剂性组分为无机金属离子时,则多使用乙醇作溶剂。
本发明提供的碳纳米管负载的NdO2催化剂,充分利用了NdO2酸性和因Nd4+/Nd3+的可逆转换而具有良好的储放氧性能及氧流动性,同时使用高比表面积且具有丰富的介孔通道的CNTS作为载体改变了NdO2的暴露晶面,进一步提高了氧流动性,进而进一步提高了催化性能,使得本发明催化剂可以在空气环境中,长时间稳定地将含氯挥发性有机物转化为H2O、CO2和HCl,使部分二甲胺与燃烧生成的NOx发生SCR反应,控制了尾气中NOx浓度。
本发明进一步提供了制备前述催化剂的方法,包括下述步骤:
首先,将一定量的可溶性钕盐和一定量的碱金属盐溶解于一定量水中,随后向溶液中加入CNTS,并将该混合物保持搅拌30分钟。然后将混合物转移至高压反应釜中并加热至130℃,并保持该温度24小时。过滤,然后将固体产物在60℃下干燥过夜,最后在高温下空气中焙烧,压片,过筛(40-60目)后即得。
在制备过程中控制各溶液的浓度和浸渍比例,使所得的碱金属改性的NdO2/CNTS催化剂具备下述特征:NdO2占催化剂重量的20-30%,碱金属占催化剂重量的0.1%~2%,余量为CNTS。本发明中,所述可溶性钕盐金属盐是指金属钕的硝酸盐、醋酸盐、氯化盐、碳酸盐、硫酸盐或草酸盐一种或几种。本发明中,步骤(2)中所述高温焙烧是指在400~600℃焙烧2~5h。
与已有技术相比较,本发明具有的技术效果是:
本发明的工艺将合成革生产干法、湿法和后处理车间废气通过沸石转轮适当浓缩后进行RCO工艺处理,二甲胺废水经吹脱塔吹脱的废气进入RCO炉催化燃烧,由于傕化剂的SCR催化效果,燃烧烟气中NOx浓度得到控制。
本发明将吸附后准备排放的气体用作二甲胺废水的吹脱气,降低了整体废气的排放量,降低了成本。
本发明提供的碳纳米管负载的NdO2催化剂,充分利用了NdO2酸性和因Nd4+/Nd3+的可逆转换而具有良好的储放氧性能及氧流动性,同时使用高比表面积且具有丰富的介孔通道的CNTS作为载体改变了NdO2的暴露晶面,进一步提高了氧流动性,进而进一步提高了催化性能,使得本发明催化剂可以在空气环境中,长时间稳定地将含氯挥发性有机物转化为H2O、CO2和HCl。
附图说明
图1为本发明的合成革工艺中废气和废液的联合处理工艺的流程示意图;
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例,都属于本发明保护的范围。
参阅图1,在一种实施例中,所采用的装置包括吸附过滤器1,转轮吸附器2,吹脱塔3,干燥塔4,RCO反应器5,管式换热器6,双向切换阀,PLC控制系统和附配风机(未画出)。
所述的工艺流程如下,废气首先经吸附过滤器1去除固体颗粒和油性雾滴,经预过滤处理的有机废气分两股进入转轮吸附器2,部分直接废气进入转轮吸附器,经分子筛吸附VOCs污染物吸附效率>90%,然后由风机导入二甲胺废液吹脱塔3;其余废气进入管式换热器6换热,升温后进入转轮脱附区,由高温废气脱附再生,所产生高浓度废气与来自二甲胺吹脱塔中的废气通过风机导入干燥塔4中,干燥后转入进入RCO反应器5中,在入口蓄热窒内吸热升温后,与催化剂床层接触进行催化燃烧反应,实现VOCs降解,该过程伴随着SCR反应(二甲胺对NOx还原)的进行,烟气中NOx含量得到了有效控制。同时从RCO反应器的燃烧室上端抽取少量烟气,通过管式换热器6对脱附废气加热。烟气流经出口蓄热室,传热后自身温度降低,由双向切换阀排出RCO反应器,通过排气筒高空排放。双向切换阀在PLC系统控制下毎2分钟切换一次,废气流向随之改变,如此循环反复从两侧进出RCO反应器,充分回收利用燃烧烟气热量。
【实施例1】
采用如图1所述工艺,其条件如下:
(1)合成革工艺废气组成:烷烃80%,丁酮10%,DMF5%,芳香烃5%。
(2)RCO反应器催化剂的制备,将11.8g硝酸钕和0.4g氯化钾溶解100mL水中,随后向溶液中加入23g CNTS纳米片,并将该混合物保持揽拌30分钟。然后将混合物转移至高压反应釜中并加热至130℃,并保持该温度24小时。过滤,然后将固体产物在60℃下干燥过夜,最后在高温下空气中焙烧,压片,过筛(40-60目)后得到23g K-NdO2/CNTS催化剂,其中NdO2质量占催化剂的31%,K占催化剂的比重为0.8%。
(3)试验主要过程如下:经预过滤处理的有机废气分两股进入转轮吸附器2,部分直接废气进入转轮吸附器,经分子筛吸附VOCs污染物吸附效率>90%,然后由风机导入二甲胺废液吹脱塔3;其余废气进入管式换热器6换热,升温后进入转轮脱附区,由高温废气脱附再生,所产生高浓度废气与二甲胺废气与来自二甲胺吹脱塔中的废气通过风机导入干燥塔4中,干燥后转入进入RCO反应器5中,在入口蓄热窒内吸热升温后,与催化剂床层接触进行催化燃烧反应,实现VOCs降解,该过程伴随着SCR反应(二甲胺对NOx还原)的进行,烟气中NOx含量得到了有效控制。同时从RCO反应器的燃烧室上端抽取少量烟气,通过管式换热器6对脱附废气加热。烟气流经出口蓄热室,传热后自身温度降低,由双向切换阀排出RCO反应器,通过排气筒高空排放,经检测二甲胺的降解率为95%,排放尾气中N2的选择性保持在87%左右。
【实施例2】
采用如图1所述工艺,其条件如下:
(1)合成革工艺废气组成:烷烃80%,丁酮10%,DMF5%,芳香烃5%。
(2)RCO反应器催化剂的制备,将11.8g硝酸钕和0.3g氯化钠溶解100mL水中,随后向溶液中加入23g CNTS纳米片,并将该混合物保持揽拌30分钟。然后将混合物转移至高压反应釜中并加热至130℃,并保持该温度24小时。过滤,然后将固体产物在60℃下干燥过夜,最后在高温下空气中焙烧,压片,过筛(40-60目)后得到23g Na-NdO2/CNTS催化剂,其中NdO2质量占催化剂的31%,Na占催化剂的比重为0.6%。
(3)试验主要过程如下:经预过滤处理的有机废气分两股进入转轮吸附器2,部分直接废气进入转轮吸附器,经分子筛吸附VOCs污染物吸附效率>90%,然后由风机导入二甲胺废液吹脱塔3;其余废气进入管式换热器6换热,升温后进入转轮脱附区,由高温废气脱附再生,所产生高浓度废气与二甲胺废气与来自二甲胺吹脱塔中的废气一起导入干燥塔4中,干燥后转入进入RCO反应器5中,在入口蓄热窒内吸热升温后,与催化剂床层接触进行催化燃烧反应,实现VOCs降解,该过程伴随着SCR反应(二甲胺对NOx还原)的进行,烟气中NOx含量得到了有效控制。同时从RCO反应器的燃烧室上端抽取少量烟气,通过管式换热器6对脱附废气加热。烟气流经出口蓄热室,传热后自身温度降低,由双向切换阀排出RCO反应器,通过排气筒高空排放,双向切换阀在PLC系统控制下毎4分钟切换一次,废气流向随之改变,如此循环反复从两侧进出RCO反应器,充分回收利用燃烧烟气热量。经检测二甲胺的降解率为96%,排放尾气中N2的选择性保持在89%左右,相比实施例1节能10%左右。
由此可见,本发明的工艺将合成革生产干法、湿法和后处理车间废气通过沸石转轮适当浓缩后进行RCO工艺处理,二甲胺废水经吹脱塔吹脱的废气进入RCO炉催化燃烧,由于傕化剂的SCR催化效果,燃烧烟气中NOx浓度得到控制。将吸附后准备排放的气体用作二甲胺废水的吹脱气,降低了整体废气的排放量,降低了成本。本发明提供的碳纳米管负载的NdO2催化剂,充分利用了NdO2酸性和因Nd4+/Nd3+的可逆转换而具有良好的储放氧性能及氧流动性,同时使用高比表面积且具有丰富的介孔通道的CNTS作为载体改变了NdO2的暴露晶面,进一步提高了氧流动性,进而进一步提高了催化性能,使得本发明催化剂可以在空气环境中,长时间稳定地将含氯挥发性有机物转化为H2O、CO2和HCl。
上述说明已经充分揭露了本发明的具体实施方式。需要指出的是,熟悉该领域的技术人员对本发明的具体实施方式所做的任何改动均不脱离本发明的权利要求书的范围。相应地,本发明的权利要求的范围也并不仅仅局限于前述具体实施方式。
Claims (4)
1.一种合成革工艺中废气和废液的联合处理工艺,其特征在于,采用如下装置,包括吸附过滤器(1),转轮吸附器(2),吹脱塔(3),干燥塔(4),RCO反应器(5),管式换热器(6)和双向切换阀(7),所述的工艺流程如下,
废气首先经吸附过滤器(1)去除固体颗粒和油性雾滴,经预过滤处理的有机废气分两股进入转轮吸附器(2),部分废气直接进入转轮吸附区,经分子筛吸附VOCs污染物,然后由风机导入二甲胺废液吹脱塔(3);其余废气进入管式换热器(6)换热,升温后进入转轮脱附区,由高温废气脱附再生,所产生高浓度废气与来自二甲胺吹脱塔中的废气通过风机导入干燥塔(4)中,干燥后转入RCO反应器(5)中,在入口蓄热窒内吸热升温后,与催化剂床层接触进行催化燃烧反应,实现VOCs降解并伴随着SCR反应的进行;烟气流经出口蓄热室,传热后自身温度降低后排出RCO反应器,通过排气筒高空排放。
2.根据权利要求1所述的合成革工艺中废气和废液的联合处理工艺,其特征在于,在转轮吸附器(2)上设置有冷却装置,在处理废气的同时不断对吸附区进行降温冷却,保证吸附区的温度稳定。
3.根据权利要求1所述的合成革工艺中废气和废液的联合处理工艺,其特征在于,吹脱塔(3)是吹脱工序的主要设备,利用二甲胺沸点低、水解呈碱性的特点,通过升温和加碱,促进二甲胺分子在填料表面由液相向气相转移,使二甲胺废水吹脫形成二甲胺废气进入后续工艺处理。
4.根据权利要求1所述的合成革工艺中废气和废液的联合处理工艺,其特征在于,废气燃烧处理前,先对RCO炉进行预热吹扫,使蓄热床屋升温至350℃,吹扫空气风量取2000Nm3/h,25℃,燃烧机功率为12~60W,散热取5%。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710701516.2A CN107261664B (zh) | 2017-08-16 | 2017-08-16 | 一种合成革工艺中废气和废液的联合处理工艺 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710701516.2A CN107261664B (zh) | 2017-08-16 | 2017-08-16 | 一种合成革工艺中废气和废液的联合处理工艺 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107261664A true CN107261664A (zh) | 2017-10-20 |
| CN107261664B CN107261664B (zh) | 2019-10-01 |
Family
ID=60077306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710701516.2A Active CN107261664B (zh) | 2017-08-16 | 2017-08-16 | 一种合成革工艺中废气和废液的联合处理工艺 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107261664B (zh) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107854959A (zh) * | 2017-12-07 | 2018-03-30 | 韩志军 | 混合型复杂工况VOCs净化工艺及装置 |
| CN111318148A (zh) * | 2020-04-23 | 2020-06-23 | 山东科源化工有限公司 | 一种二甲胺或三甲胺尾气用于蓄热式高温氧化炉除硝装置及方法 |
| CN113578023A (zh) * | 2021-08-03 | 2021-11-02 | 福建省福能龙安热电有限公司 | 一种利用二甲胺废液处理锅炉废气中氮氧化物的方法及装置 |
| CN114484471A (zh) * | 2022-02-18 | 2022-05-13 | 浙江陕鼓能源开发有限公司 | 一种合成革高浓度dmf废液中三废资源化利用系统和工艺 |
-
2017
- 2017-08-16 CN CN201710701516.2A patent/CN107261664B/zh active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107854959A (zh) * | 2017-12-07 | 2018-03-30 | 韩志军 | 混合型复杂工况VOCs净化工艺及装置 |
| CN111318148A (zh) * | 2020-04-23 | 2020-06-23 | 山东科源化工有限公司 | 一种二甲胺或三甲胺尾气用于蓄热式高温氧化炉除硝装置及方法 |
| CN113578023A (zh) * | 2021-08-03 | 2021-11-02 | 福建省福能龙安热电有限公司 | 一种利用二甲胺废液处理锅炉废气中氮氧化物的方法及装置 |
| CN113578023B (zh) * | 2021-08-03 | 2022-05-17 | 福建省福能龙安热电有限公司 | 一种利用二甲胺废液处理锅炉废气中氮氧化物的方法及装置 |
| CN114484471A (zh) * | 2022-02-18 | 2022-05-13 | 浙江陕鼓能源开发有限公司 | 一种合成革高浓度dmf废液中三废资源化利用系统和工艺 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107261664B (zh) | 2019-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN208824192U (zh) | 一种VOCs废气高效吸附脱附催化燃烧处理系统 | |
| CN105371286A (zh) | 一种净化挥发性有机废气的预热式催化燃烧系统 | |
| CN107261664B (zh) | 一种合成革工艺中废气和废液的联合处理工艺 | |
| CN103331086A (zh) | 可移动一体式有机废气处理装置 | |
| CN104492255A (zh) | 一种采用吸附-臭氧催化伴随吸附材料原位再生处理废气的方法 | |
| CN205782992U (zh) | 一种有机废气处理装置 | |
| CN111689497B (zh) | 可抑制二噁英生成的危险废炭节能活化再生系统 | |
| CN108786449A (zh) | 一种新型V0Cs吸附活化脱附低温催化处理方法及其处理装置 | |
| CN112742181A (zh) | 一种VOCs废气处理系统及方法 | |
| CN206660779U (zh) | 一种废气治理系统 | |
| CN205672742U (zh) | 一种有机气体治理装置 | |
| CN103316586B (zh) | 一种净化气体中有机污染物的装置及方法 | |
| CN106237800A (zh) | 挥发性有机物废气熔盐氧化系统 | |
| CN110170232A (zh) | Voc吸附浓缩催化燃烧系统 | |
| CN112691542B (zh) | 一种用于吸附-催化氧化VOCs的金属复合分子筛材料及其制备方法与应用 | |
| CN101920152B (zh) | 处理大气量工业废气中有机物的方法 | |
| EP1726565A1 (en) | Carbon material and flue gas treatment apparatus | |
| CN106139840A (zh) | 含低浓度voc废气的净化装置及方法 | |
| CN107433104A (zh) | 一种基于roc技术的废气净化工艺 | |
| CN107362681B (zh) | 一种合成革工艺中废气和废液的高效催化处理工艺 | |
| CN107308814B (zh) | 一种自控型废气和废液的处理工艺 | |
| CN111686706B (zh) | 负压封闭式危险废炭节能活化再生系统 | |
| CN106807188A (zh) | 一种废气处理工艺 | |
| CN113019121A (zh) | 一种生活垃圾焚烧厂低温scr烟气脱硝装置 | |
| KR102483839B1 (ko) | 소각장폐열을 이용하여 활성탄허니컴필터를 재생 처리하기 위한 휘발성유기화합물 처리시스템 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191217 Address after: 226400 science and Technology City, Rudong Coastal Economic Development Zone, Nantong, Jiangsu Patentee after: NJU Environmental Protection Technology Services Nantong Co., Ltd. Address before: 311800 Shaoxing City, Zhejiang, Zhuji Datang Town, Wenchang Road, No. 108 Wenchang Patentee before: Xuan Yaohang |
|
| TR01 | Transfer of patent right |