CN101507932A - Preparation method of material capable of removing hydrogen sulphide and thiol - Google Patents
Preparation method of material capable of removing hydrogen sulphide and thiol Download PDFInfo
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- CN101507932A CN101507932A CNA2008100797738A CN200810079773A CN101507932A CN 101507932 A CN101507932 A CN 101507932A CN A2008100797738 A CNA2008100797738 A CN A2008100797738A CN 200810079773 A CN200810079773 A CN 200810079773A CN 101507932 A CN101507932 A CN 101507932A
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- Prior art keywords
- hydrogen sulfide
- carrier
- resin
- mercaptan
- heavy metal
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims description 24
- 239000000463 material Substances 0.000 title abstract description 34
- 125000003396 thiol group Chemical class [H]S* 0.000 title 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 43
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 229920005989 resin Polymers 0.000 claims description 41
- 239000011347 resin Substances 0.000 claims description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000000835 fiber Substances 0.000 claims description 23
- 150000002500 ions Chemical class 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003456 ion exchange resin Substances 0.000 claims description 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 7
- -1 phenolic aldehyde Chemical class 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 4
- 239000003729 cation exchange resin Substances 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 150000003440 styrenes Chemical class 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 3
- 239000002250 absorbent Substances 0.000 claims description 3
- 230000002745 absorbent Effects 0.000 claims description 3
- 239000003957 anion exchange resin Substances 0.000 claims description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000007385 chemical modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 238000009423 ventilation Methods 0.000 claims description 3
- 238000006424 Flood reaction Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000009920 chelation Effects 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000005342 ion exchange Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 10
- 229910052802 copper Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229920001429 chelating resin Polymers 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- ORMNPSYMZOGSSV-UHFFFAOYSA-N dinitrooxymercury Chemical compound [Hg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ORMNPSYMZOGSSV-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003317 industrial substance Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 208000028571 Occupational disease Diseases 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 244000245420 ail Species 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-N sodium;hydron;carbonate Chemical compound [Na+].OC(O)=O UIIMBOGNXHQVGW-UHFFFAOYSA-N 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
The invention relates to a method for preparing a material which can remove hydrogen sulfide and mercaptan at the same time. A carrier containing one or more of functional groups of -SO3<->, -COOH, -COO<-> and -NHx is soaked in a solution of heavy metal and stirred, and the carrier is picked up, washed by waster and put in a ventilated place for natural drying to obtain the material. By adopting the ion exchange and/or chelation technology, the metal ion is fixed on the surface of the carrier to prepare the material, so that the material has the characteristics of stable active components, difficult loss of active components, big adsorption quantity and good dynamic performance, and can quickly and thoroughly remove the hydrogen sulfide and mercaptan in high efficiency.
Description
Technical field
The present invention relates to a kind ofly can be used for removing in the gas simultaneously or the preparation method of the solid material of hydrogen sulfide and mercaptan in the liquid, belong to field of material preparation.
Background technology
Hydrogen sulfide has the rotten egg smell, and mercaptan has strong garlic smell, and its threshold of feelings is respectively 0.0005mg/m
3And 0.0002mg/m
3Even gas concentration is very low in the air, also can smell strong stink.Hydrogen sulfide and mercaptan are harmful, and they all can stimulate people's central nervous system, and symptom such as can produce headache when concentration is low, feel sick is when concentration is high even also can cause the respiratory system paralysis and death.In the air that contains hydrogen sulfide and/or mercaptan, work, serious harm the health of human body.The concentration of China's workshop air sanitary standard regulation hydrogen sulfide can not surpass 10mg/m
3, and formulated relevant Chinese diagnosis of occupational disease national standard---" management of occupational acute hydrogen sulfide poisoning diagnostic criteria ".The former Soviet Union also stipulates the maximum permissible concentration 1mg/m of ethyl mercaptan in the workshop air
3Hydrogen sulfide seldom uses industrial, and the hydrogen sulfide of contact mostly is the product of chemical reaction or protein natural degradation or exists with the impurity form; Mercaptan can be used as the raw material etc. of intermediate, thiofide or the bactericide of some medicines, but in most cases, mercaptan is unwanted, the waste gas that is produced in the exploitation of base oil and refining, coal gasification and the gas extraction process often contains mercaptan, it need be removed to reach the environmental emission standard during discharging.
The methods of oxidation that adopt are removed hydrogen sulfide and/or mercaptan more in the industrial production, and sewage treatment plant adopts hypochlorous acid or potassium permanganate that hydrogen sulfide is become the higher sulfur dioxide of the threshold of feelings with mercaptan oxidation more, to reduce airborne stink.Yet sulfur dioxide is the main component of acid rain, adopts this method removing hydrogen sulfide and/or mercaptan easily to cause air secondary to pollute.
Chinese patent CN 200580018146.8, " method of removing that comprises hydrogen sulfide and mercaptan sulfides " discloses a kind of method that can remove hydrogen sulfide and mercaptan simultaneously, promptly use 2-bromo-2-nitro the third-1,3-glycol diacetate absorbing hydrogen sulphide or mercaptan sulfides, thereby with its removing.The method that this method adopts liquid to absorb is removed hydrogen sulfide and mercaptan, and absorption plant is bigger, carries absorption liquid in the exit gas easily secretly, causes secondary pollution.
The method of single clear hydrogen sulfide or mercaptan is more, disclose three kinds of methods of removing hydrogen sulfide respectively as " removing the method for hydrogen sulfide ", " by reclaiming sulphur in the hydrogen sulfide containing gas " and " hydrogen sulfide in the oxidation removal gas ", they all are to utilize the redox character of hydrogen sulfide to adopt different oxidants to remove hydrogen sulfide; " have the copper carboxylate type resin material that removes the mercaptan effect ", " polymeric material with dethiol action ", " a kind of regenerable resin material with dethiol action ", " having cellulosic material of dethiol action and preparation method thereof " four patents disclose four kinds of materials with dethiol action respectively.These four patents have similitude, and they have protected the material that can be used for removing mercaptan of the method preparation that loads bivalent cupric ion on the carrier of different shape respectively.The material or the method for seven above-mentioned patent disclosures can only be removed single material.Adopt single method to remove hydrogen sulfide and mercaptan expense height, apparatus is big, and is uneconomical.
Summary of the invention:
In order to overcome the shortcoming of prior art, the invention provides a kind of preparation methods that can remove hydrogen sulfide and mercaptan simultaneously, its stable performance, safe and reliable, simple to operate, easily realize suitability for industrialized production, can remove in the gas simultaneously or the solid material of hydrogen sulfide and/or mercaptan in the liquid.The workshop stink that this material can be used for removing that oil exploitation is refining, papermaking, chemical fertilizer manufacturing, chemical fibre manufacturing and some industrial chemicals manufacturing etc. can produce hydrogen sulfide and/or mercaptan industry; At the bottom of also available this material is done adsorbent preparation and is fit to coal mine, the mask worn of special occasions operating personnel such as sewer; Can also be that adsorbent prepares the deodorizing air purifier with this material, be used to remove the stink of indoor toilets.
The present invention is a kind of solid material that can remove hydrogen sulfide and mercaptan simultaneously that utilizes ionic bond and/or coordinate bond effect that carrier and heavy metal ion are combined and be prepared from.This material is to contain-SO
3 -,-COOH ,-COO
-And/or-NH
xThe solid of group is a carrier, is the activated centre with the heavy metal ion, and carrier is immersed in the heavy metal ion solution, after the taking-up, washes with water and dries naturally in the ventilation and be prepared from.
A kind of carrier that can remove the material of hydrogen sulfide and mercaptan simultaneously can be resin, fiber or active carbon.The resin type carrier can be that faintly acid PMA cationoid exchanger resin, faintly acid polymethyl methacrylate cationoid exchanger resin, faintly acid polyacrylonitrile resinoid, faintly acid carboxylic acid type phenolic aldehyde are ion exchange resin, strong-basicity styrene series cationic ion-exchange resin, polystyrene chelating ion exchange resin, alkalescent epoxy type anion exchange resin; The fibrous type carrier can be the faintly acid polyacrylonitrile fibre and the alkalescent polyacrylonitrile fibre of modification; Absorbent charcoal carrier can be the faintly acid active carbon and the alkalescent active carbon of chemical modification.
The resin type carrier can also be according to Chinese patent " a kind of chelating resin and the synthetic method " (patent No.: the CN02129052.0) vector resin of disclosed method preparation.This method discloses a kind of containing-COO
-With-NH
xThe preparation method of chelating resin, be about to the macroreticular resin exchange and go up heavy metal ion; Utilize the chelating ability of heavy metal ion and macromolecule amine, the macromolecule amination is adsorbed onto the macroreticular resin matrix surface; The macromolecule amine that utilizes the polyaldehyde crosslinking agent will be adsorbed on the macroreticular resin matrix surface is cross-linked with each other, securely attached on the matrix resin; Last soda acid wash-out typing, obtain to contain-COO-and-NH
xThe resin type carrier.
The fibrous type carrier can also be according to " a kind of chelating function fiber and the synthetic method " (patent No.: the CN02129051.2) carrier fibre of disclosed method preparation.This method discloses a kind of containing-COO
-With-NH
xThe preparation method of chelate fibre, promptly at matrix acrylic fiber surface chemistry coating last layer polymine, and make polymine stably anchor at fiber surface by crosslinking agent to make.
A kind of activated centre heavy metal ion that can remove the material of hydrogen sulfide and mercaptan simultaneously, its solution can be Cu
2+, Zn
2+, Fe
2+, Pb
2+, Cu
+, Ag
+, Hg
2+, or Cu
2+, Zn
2+, Fe
2+, Pb
2+, Cu
+, Ag
+, Hg
2+In any mixed solution of two or more ion arbitrary proportions.
The invention provides a kind of resin material that can remove hydrogen sulfide and mercaptan simultaneously with the preparation method, this solid material is to contain-SO
3 -,-COOH ,-COO
-,-NH
xIn the solid matter of one or more functional groups be carrier, be the activated centre with the heavy metal ion, between carrier and the heavy metal ion with ionic bond and/or coordinate bond combination.This method is that carrier is immersed in a period of time in the heavy metal solution of finite concentration and solid-to-liquid ratio, ceaselessly stirs; After the taking-up, wash resin with water, and place the ventilation to dry naturally to be prepared from.
The carrier of this material can be resin, fiber or active carbon.The resin type carrier can be that faintly acid PMA cationoid exchanger resin, faintly acid polymethyl methacrylate cationoid exchanger resin, faintly acid polyacrylonitrile resinoid, faintly acid carboxylic acid type phenolic aldehyde are ion exchange resin, strong-basicity styrene series cationic ion-exchange resin, polystyrene chelating ion exchange resin, alkalescent epoxy type anion exchange resin; The fibrous type carrier can be the faintly acid polyacrylonitrile fibre and the alkalescent polyacrylonitrile fibre of modification; Absorbent charcoal carrier can be the faintly acid active carbon and the alkalescent active carbon of chemical modification.The activated centre heavy metal ion can be Cu
2+, Zn
2+, Fe
2+, Pb
2+, Cu
+, Ag
+, Hg
2+, also can be the mixture of the arbitrary proportion of above-mentioned metal ion.The heavy metal ion solution concentration can be 0.01～35%, and concentration is lower than 0.01%, and the material activity center that is prepared into is less, removes poor-performing; Concentration is higher than 35%, then can cause unnecessary waste, and wherein Zui You concentration range is 1～15%.The time that carrier floods in heavy metal solution can be 10min～10h, contains the heavy metal ion that body can adsorb appropriate amount between at this moment, has guaranteed that material removes the performance of hydrogen sulfide and mercaptan.The ratio (solid-to-liquid ratio) of the volume of the volume of vector resin and heavy metal ion solution can be 1:15～150, and when being lower than 1:15, carrier soaks into not saturating, causes finished-product material heavy metal activated centre skewness; Be higher than 1:150, then can increase the treating capacity of waste liquid, contaminated environment.
The present invention has following advantage: (1) raw material source is abundant, and preparation technology is simple, and preparation process is controlled easily; (2) adopting heavy metal ion is the activated centre, and material is removed effect stability, and dynamic performance is better, and is safe and reliable; (3) utilize fixedly heavy metal ion of ionic bond and/or coordinate bond, activated centre stable performance, difficult drop-off; (4) product form is various, can be prepared into fibrous type, resin type or active carbon type material according to user's demand; (5) aspect air cleaning, the filter core that can be used as air purifier, oil exploitation is refining in order to remove, papermaking, chemical fertilizer manufacturing, chemical fibre manufacturing and some industrial chemicals manufacturing etc. can produce the workshop stink of hydrogen sulfide and/or mercaptan industry or the stink between domestic hygiene; (6) aspect special material prepares, this material can be used as the packing material of the mouth mask that special occasions uses.
Its carrier of material provided by the present invention can also be to contain can change into-SO
3 -,-COOH ,-COO
-And/or-NH
xThe resin of group, fiber or active carbon.
Specific embodiment
The preparation of A, material
Embodiment 1
Take by weighing 5g commercially available-COOH type D113 resin (acidulous acrylic acid's cation exchanger resin), be immersed in 35% the copper-bath, time 5h, solid-to-liquid ratio is 1:15, ceaselessly stirs; After taking out resin, water cleans and dries naturally, and obtaining copper content is the resin of copper of 3.4mmol/g.
Embodiment 2
Weighing 5g Amberlite XAD-7HP (PMA class polymeric adsorbent) puts into conical flask, and to the NaOH solution 150mL that wherein adds 5%, hydrolysis 1h under 100 ℃ of conditions, water suction filtration clean to neutral, acquisition-COO
-The type vector resin.It is in 5% the solution of zinc sulfate that this vector resin is immersed in concentration, time 3h, and solid-to-liquid ratio is 1:50, ceaselessly stirs; After taking out resin, water cleans and dries naturally, and obtaining zinc content is the zinc resin of 0.8mmol/g.
Embodiment 3
Will according to Chinese patent " a kind of chelating resin and synthetic method " preparation-COO
-,-NH
xThe type carrier is immersed in concentration and is in 0.01% the liquor argenti nitratis ophthalmicus, time 2h, and solid-to-liquid ratio is 1:150, ceaselessly stirs; After taking out resin, water cleans and dries naturally, and obtaining silver content is the silver resin of 1.0mmol/g.
Embodiment 4
Take by weighing 5g commercially available-N (COO
-)
2Type D751 resin (polystyrene chelating ion exchange resin) is immersed in 1% the copper-bath, time 10h, and solid-to-liquid ratio is 1:75, ceaselessly stirs; After taking out resin, water cleans and dries naturally, and obtaining copper content is the resin of copper of 0.25mmol/g.
Embodiment 5
Take by weighing 5g strong-basicity styrene series cationic ion-exchange resin, be immersed in 20% the cuprous chloride solution, time 5h, solid-to-liquid ratio is 1:60, ceaselessly stirs; After taking out resin, water cleans and dries naturally, and obtaining copper content is the cuprous resin of 1.8mmol/g.
Embodiment 6
With 1g according to Chinese patent " a kind of chelating function fiber and synthetic method " preparation-COO
-,-NH
xThe type carrier fibre is immersed in concentration and is in 3% the copper-bath, time 10min, and solid-to-liquid ratio is 1:100, ceaselessly stirs; After taking out fiber, water cleans and dries naturally, and obtaining copper content is the copper fiber of 0.45mmol/g.
Embodiment 7
Take by weighing 1g and contain-the faintly acid polyacrylonitrile fibre of COOH functional group, be immersed in concentration and be in 15% the solution of zinc sulfate, time 8h, solid-to-liquid ratio is 1:50, ceaselessly stirs; After taking out fiber, water cleans and dries naturally, and obtaining zinc content is the zinc fiber of 2.5mmol/g.
Embodiment 8
Take by weighing 3g faintly acid active carbon, be immersed in concentration and be in 8% the solution of ferrous chloride, time 10h, solid-to-liquid ratio is 1:120; After taking out active carbon, water cleans and dries naturally, and obtaining iron-holder is the ferrous active carbon of 3.1mmol/g.
Embodiment 9
Take by weighing 3g faintly acid active carbon, be immersed in concentration and be in 5% the lead acetate solution, time 6h, solid-to-liquid ratio is 1:100; After taking out active carbon, water cleans and dries naturally, and obtaining lead tolerance is the plumbous active carbon of 1.2mmol/g.
Embodiment 10
Take by weighing 3g faintly acid active carbon, be immersed in concentration and be in 0.5% the mercuric nitrate solution, time 8h, solid-to-liquid ratio is 1:90; After taking out active carbon, water cleans and dries naturally, and obtaining mercury content is the mercury active carbon of 0.6mmol/g.
Embodiment 11
Take by weighing 3g alkalescent active carbon, be immersed in copper ion concentration and be 3%, zinc ion concentration is in 2% the solution, time 5h, solid-to-liquid ratio is 1:30; After taking out active carbon, water cleans and dries naturally, and the acquisition copper content is that 0.3mmol/g, zinc content are the active carbon of 0.2mmol/g.
B, foul smell are removed experiment
1 in the airtight glass container of 30L, injects 10mL/m
3Foul smell, and measure the concentration of residual gas.Be blank constituent concentration.
2 materials that 5g is prepared according to A are placed in the airtight glass container of 30L, inject 10mL/m
3Foul smell, open agitation fan operation 10min, in container, gas is sampled behind the 30min, and measures residual gas concentration.Be remaining constituent concentration.
Deodorizing rate (%)=[(the blank constituent concentration of foul smell-remaining foul smell constituent concentration)/blank constituent concentration of foul smell] * 100%
Table 1 has provided the effect of different kind of material removing hydrogen sulfide and mercaptan.
Table 1
Claims (8)
1, a kind of preparation methods that can remove hydrogen sulfide and mercaptan simultaneously is characterized in that: will contain-SO
3 -,-COOH ,-COO
-,-NH
xIn the carrier of one or more functional groups be immersed in the heavy metal solution, stir, take out carrier, wash with water and place the ventilation to dry naturally and get final product.
2, the preparation methods of removing hydrogen sulfide and mercaptan simultaneously according to claim 1 is characterized in that: described carrier is for containing-SO
3 -,-COOH ,-COO
-,-NH
xIn resin, fiber or the active carbon of one or more functional groups.
3, the preparation methods of removing hydrogen sulfide and mercaptan simultaneously according to claim 2 is characterized in that: described resin type carrier is that faintly acid PMA cationoid exchanger resin, faintly acid polymethyl methacrylate cationoid exchanger resin, faintly acid polyacrylonitrile resinoid, faintly acid carboxylic acid type phenolic aldehyde are ion exchange resin, strong-basicity styrene series cationic ion-exchange resin, polystyrene chelating ion exchange resin or alkalescent epoxy type anion exchange resin; Faintly acid polyacrylonitrile fibre that described fibrous type carrier is modification or weakly alkaline polyacrylonitrile fibre; Described absorbent charcoal carrier is the faintly acid active carbon or the alkalescent active carbon of chemical modification.
4, the preparation methods of removing hydrogen sulfide and mercaptan simultaneously according to claim 1 is characterized in that: described heavy metal ion is Cu
2+, Zn
2+, Fe
2+, Pb
2+, Cu
+, Ag
+, Hg
2+In any one or multiple.
5, according to claim 1 or the 4 described preparation methods of removing hydrogen sulfide and mercaptan simultaneously, it is characterized in that: described heavy metal ion solution concentration is 0.01～35%.
6, the preparation methods of removing hydrogen sulfide and mercaptan simultaneously according to claim 5 is characterized in that: described heavy metal ion solution concentration is 1～15%.
7, the preparation methods of removing hydrogen sulfide and mercaptan simultaneously according to claim 1, it is characterized in that: the time that described carrier floods in heavy metal solution is 10min～10h.
8, the preparation methods of removing hydrogen sulfide and mercaptan simultaneously according to claim 1 is characterized in that: the volume of described carrier is that solid-to-liquid ratio is 1:15～150 with the ratio of the volume of heavy metal ion solution.
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| CNA2008100797738A CN101507932A (en) | 2008-11-09 | 2008-11-09 | Preparation method of material capable of removing hydrogen sulphide and thiol |
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|---|---|---|---|
| CNA2008100797738A CN101507932A (en) | 2008-11-09 | 2008-11-09 | Preparation method of material capable of removing hydrogen sulphide and thiol |
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|---|---|
| CN101507932A true CN101507932A (en) | 2009-08-19 |
Family
ID=41000559
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|---|---|---|---|
| CNA2008100797738A Pending CN101507932A (en) | 2008-11-09 | 2008-11-09 | Preparation method of material capable of removing hydrogen sulphide and thiol |
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| CN102617281A (en) * | 2011-01-28 | 2012-08-01 | 株式会社大赛璐 | Method for removing sulfur compound from alcohol |
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| CN103506071A (en) * | 2012-06-19 | 2014-01-15 | 中国石油化工股份有限公司 | Purificant used for absorbing hydrogen sulfide and carbonyl sulfide in tail gas of natural gas and preparation method thereof |
| CN109310982A (en) * | 2016-06-28 | 2019-02-05 | 株式会社可乐丽 | Composition for removing sulfur-containing compounds |
| US11291947B2 (en) | 2016-06-28 | 2022-04-05 | Kuraray Co., Ltd. | Composition for removing sulfur-containing compound |
| CN110475598A (en) * | 2017-06-11 | 2019-11-19 | Msa技术有限公司 | Filter for sulphur compound |
| CN111715031A (en) * | 2020-06-24 | 2020-09-29 | 江西师范大学 | A carbon dioxide absorption medium and its optimization process |
| CN115301297A (en) * | 2022-08-02 | 2022-11-08 | 陕西海斯夫生物工程有限公司 | Cation exchange resin loaded with nano silver particles, preparation method and application thereof |
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