CN104624223B - A kind of continuous dearsenic catalyst for industrial tail gas purification and preparation method thereof - Google Patents
A kind of continuous dearsenic catalyst for industrial tail gas purification and preparation method thereof Download PDFInfo
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Abstract
The present invention announces a kind of continuous dearsenic catalyst for industrial tail gas purification, using molecular sieve as carrier, is made up of active component solution, molecular screen primary powder and bonding dispersant extruded moulding, active component is mantoquita.Wherein, carrier sieves for 13X granulin molecules, and effective aperture is 0.8~1.5nm, and wherein micro pore volume accounting is more than 80%；Molecular screen primary powder is weighed first, and stirring adds active component solution, and material adds cohesive dispersant in after wetting state, and all materials are well mixed, and are made after extruded moulding, drying and roasting；For removing arsenic hydride in the atmosphere such as calcium carbide tail gas, yellow phosphoric tail gas, make arsenic hydride that hydration reaction occur after being oxidized by catalysis oxidation, then exported with arsenic acid or arsenious acid.The active component of continuous dearsenic catalyst does not have significant change before and after catalytic oxidation, can meet that the CO in tail gas makees the demand of high value added product.
Description
Technical field
The present invention relates to the purification of arsenic hydride in industrial tail gas, more particularly to a kind of continuous dearsenification being used in industrial gasses
Catalyst and preparation method thereof.
Background technology
Arsenic hydride is a kind of colourless, hypertoxic, and density is more than the gas of air, and arsenic is all contained in many smelting exhausts
Hydrogen.Also all contain arsenide as contained in iron ore in arsenic iron, calcium phosphate ore, calcium carbide, these ores containing arsenide are in humidity
Or under the conditions of having vapor existing, by heating, arsenide is just present in industrial tail gas in the form of arsenic hydride.Closed
During stove production calcium carbide, 1t calcium carbides, about by-product 400m are often produced3Tail gas.In calcium carbide tail gas the content of arsenic hydride be 200~
800mg/m3, CO contents are about 80%.The calcium carbide production capacity in China in 2013 is 37,900,000 tons, and actual production is 22,340,000 tons, real
The m of border by-product calcium carbide tail gas 8,900,000,0003, wherein fuel is done in about 70% cooperation calcium carbide production is used for lime burning, 6% is used to make waste heat pot
The tail gas of the fuel of stove, also at least more than 12%, about 1,000,000,000 m3The burned emptying of tail gas, this is a kind of wave on the energy
Take, while certain pollution is also result in environment.During phosphorus production, CO 90%, sulphur are contained in the yellow phosphoric tail gas of by-product
Change 2000~3000mg/m of hydrogen3, 1000~2000mg/m of hydrogen phosphide3, 200~800mg/m of arsenic hydride3, hydrogen fluoride 100~
600mg/m3, other are CO2、H2、N2、H2O etc..The yellow phosphorus production capacity in China in 2013 is 1,800,000 tons/year, annual actual production
Close to 1,000,000 tons, the output phosphor in the whole world more than 80% has been concentrated.Often produce 1t yellow phosphorus about by-product 2700m3Yellow phosphorus tail
Gas, wherein 20% coordinates production to be used for raw material stoving, other 80% about 2,100,000,000 m3Yellow phosphoric tail gas emptying burning.Arsenic hydride is at it
Also there is presence in his industrial smelting exhaust, because CO contents are higher in these smelting exhausts, industrial application value is very high, but by
Application scenario is can not find in the presence of the impurity such as these sulphur, phosphorus, arsenic.The purification of sulphur, phosphorus has more ripe technology at present, and
Also there are problems in the purification of arsenic hydride, the industrialization amplification, clean-up effect such as purification technique are held in actual applications
Continuous property etc..The purification techniques of industrial tail gas is the precondition using these tail gas, and high added value is done especially with CO resources
One chemical products of carbon when, the presence of arsenic hydride can cause synthetic catalyst irreversible " poisoning ", and then cause synthesis catalytic
The failure of agent.
Arsenide has a presence in ore and many industrial tail gas, also there is very purification method used by different occasions
Big difference.It is extractant that publication number CN1265373A, which discloses one kind using carbon tetrachloride or chloroform, and EDTA and disodium salt are
Complexing agent, DDTC-X are that chelating agent can purify arsenic ion in yellow phosphorus under conditions of pH value 4~6, temperature 50 C~70 DEG C
Method；This method is suitable for purifying the arsenide in solid matter yellow phosphorus.Patent CN1076173A is disclosed in a kind of hydrogen stream
The Immesion active carbon preparation method of purifying hydrogen phosphide, arsenic hydride, it is characterised in that using coal mass active carbon as carrier, dipping Cu, Hg,
Tetra- kinds of metallic compounds of Cr, Ag, the catalyst can be used for the removing of arsenic hydride in hydrogen atmosphere or air atmosphere.The catalyst has
There is the capacity of larger absorption arsenic hydride, it is necessary to regenerate after arsenic hydride penetrates, in addition in addition to Cu, the poison of remaining three kinds of metals
Property it is all very big, if industrialized production, in maceration extract the processing of waste metal ion can also turn into a problem.Publication number
The method of arsenic hydride in a kind of purifying industrial waste gases of CN101402020A patents state, by using phthalocyanine cobalt liquor with
One or more in Fe3+, Ni2+, Mn2+ are modified by dipping method to finished product molecular sieve, modified molecular sieve catalyst
The arsenic hydride of 500~1600mg/m3 in gas can be reduced to 0.3mg/m3 or so.Catalyst is modified liquid and prepared so first
Impregnated again afterwards, last drying and roasting, preparation technology is the flow of general impregnated catalyst.After catalyst operation a period of time
Need to regenerate, the catalyst inactivated after purification rinses 3~6h with vapor, then dries under 100 DEG C~150 DEG C temperature conditionss
Regenerated catalyst is just obtained after 12h, the regeneration efficiency of catalyst is more than 90%.The condition of patents state catalyst regeneration and
Regenerate an efficiency still more than 90%, but the document do not refer to catalyst regenerate again after loss in efficiency, do not celebrate the birthday
Life experiment, industrialization amplification are also faced with some problems.Publication number CN101602642A patent report is a kind of to be used for propylene, second
Cleanser of alkene light hydrocarbon materials dearsenification and preparation method thereof.The cleanser is using aluminum oxide as carrier, and cupric oxide is active component, oxygen
Change zinc is auxiliary agent.For the saturation arsenic capacity of the cleanser up to 30%, industrial arsenic capacity can reach 15%.But the cleanser uses
Be still dipping method.The patent of Publication No. 102806065 is disclosed for adsorbing arsenic hydride and phosphatization in alkene tail gas
The preparation method of hydrogen purification agent, the cleanser using activated carbon as carrier impregnation potassium permanganate, mantoquita and zinc salt mixed solution
In be prepared.The method of the patent is similar with patent No. CN101602642A method, and simply carrier is changed to by aluminum oxide
Activated carbon.It is by cleanser made from the method for carrier impregnation or catalyst above, belongs to dry cleaning arsenic hydride.It is open
Number for CN102389697A a kind of method of removing arsenic hydride in tail gas of iron making blast furnace by wet process of patent report.This method will refine
Iron blast furnace tail gas is passed through the reaction tower containing sodium hypochlorite, utilizes sodium hypochlorite through washing with after alkali cleaning dedusting and sour gas
The arsenic hydride that strong oxidation is removed in tail gas reaches the purpose of cleaning of off-gas, and an important step of this method is to need to remove
Acidic materials in gas, as contained H in yellow phosphoric tail gas2S、CO2Deng the presence of these acidic materials just have impact on arsenic hydride
Removing.Publication number 102311301A patent discloses the method using arsenic hydride in copper salt solution removing gaseous ethene, propylene,
Bromine water, hydrogen peroxide, copper salt solution three-level pair is respectively adopted using the arsenic hydride in the method removing gas of liquid phase scrubbing in this method
Arsenic hydride absorb and detection gas outlet arsenic hydride concentration.The absorbing liquid species that the patent uses is more, and these solution exist
All it is consumptive during removing arsenic hydride, needs to change the processing of new soln, in use old solution after penetrating
Also bring along the problem of certain.
In summary, although the method for removing arsenic hydride is a lot, these methods all face during industrialized use
Face problems.At present, the problem of dry method dearsenification cleanser is present mainly has two：1) purification prepared using dipping method
Agent, impregnating metal species is more, and because Metal is big, industrial production and liquid waste processing have certain concentration；2) prepare
Hydrodearsenic Catalyst there is certain adsorption capacity, arsenic hydride to need to regenerate after penetrating, regeneration technology is cumbersome, and the efficiency after regeneration only has
90% or so, cleanser restricted lifetime.Wet method dearsenication exist used in oxidant species it is more, and arsenic hydride penetrate after also to face
The problem of liquid waste processing.So field of gas purification needs to develop new dearsenic catalyst capable of being industrialized.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the present invention provides a kind of continuous dearsenification applied to industrial tail gas purification
Catalyst and its preparation technology, for removing arsenic hydride in the atmosphere such as calcium carbide tail gas, yellow phosphoric tail gas, done with the CO met in tail gas
The demand of high value added product.
The present invention principle be：The present invention provides a kind of continuous dearsenic catalyst applied to industrial tail gas purification.In order to
The complex operations for avoiding catalyst repeated regeneration from bringing, it is contemplated that the catalyst regeneration efficiency of dry method catalysis arsenic hydride is with regeneration time
Number decay, and then make the reduction of catalyst service life, it can be avoided on a catalyst by product after continuously exporting oxidation
Absorption, it is ensured that the continuous operation of catalyst.It can design according to this requirement and principle, catalyst and be prepared as molecular sieve catalyst, should
Molecular sieve catalyst is bigger than surface, is mainly distributed with micropore.Arsenic hydride is easily reacted in catalyst surface, but is not adsorbed
In on catalyst, but beds are exported in a manner of the dilute arsenic acid mixed vapour of low boiling in the presence of vapor.This
The arsenic hydride that the catalyst provided can be under certain process conditions in continuous catalysis removing industrial tail gas is invented, catalyst then can be
Successive reaction under this process conditions, without regeneration, and the catalyst resistant to sulfur, resistance to phosphorus are adapted to the gas such as yellow phosphoric tail gas, calcium carbide tail gas
Atmosphere.
Technical scheme provided by the invention is：
It is a kind of for industrial tail gas purification continuous dearsenic catalyst, the continuous dearsenic catalyst using molecular sieve as carrier,
It is made up of active component solution, molecular screen primary powder and bonding dispersant extruded moulding, the active component is mantoquita.
Above-mentioned continuous dearsenic catalyst, carrier be 13X granulin molecules sieve, its effective aperture is 0.8~1.5nm, mainly with
Micropore is distributed；It is 650~720m than surface2/g；Total pore volume is 0.34~0.39cm3/ g, wherein micro pore volume accounting exceed
80%.
The active component of above-mentioned continuous dearsenic catalyst is specially copper nitrate or copper chloride；Catalyst uses catalytic oxidation
Reacted with the arsenic hydride in tail gas, can make arsenic hydride that following reaction occur by this catalyst：
2AsH3+4O2→As2O5+H2O
2AsH3+3O2→As2O3+3H2O
As2O5+3H2O→2H3AsO4
As2O3+3H2O→2H3AsO3
2H3AsO4→2H3AsO3+O2
After arsenic hydride is oxidized to arsenic trioxide or diarsenic pentoxide, hydration reaction occurs with the vapor being added,
Beds are finally exported in the form of arsenic acid or arsenious acid, the gas after export is entered through spraying cooling, arsenide by gas phase
Enter liquid phase, liquid is run by the way of circulated sprinkling absorption, after arsenate concentration reaches certain value in liquid phase, adds hydroxide
Calcium carries out precipitation and focused on.Product after arsenic hydride is oxidized does not adsorb in catalyst surface but exports bed with reaction gas flow
Layer, catalyst do not have significant change during the course of the reaction, and this catalyst can be carried out continuously the removing of arsenic hydride.
The active component of above-mentioned continuous dearsenic catalyst is detected before and after catalytic oxidation by X-ray diffractometer, is sent out
Significant change is now had no, its form keeps stable in yellow phosphoric tail gas, calcium carbide stove exhaust atmosphere.
The present invention also provides the preparation method of above-mentioned continuous dearsenic catalyst, comprises the following steps：
1) active component solution is configured, wherein active component is mantoquita；
2) molecular screen primary powder is weighed, active component solution is added into molecular screen primary powder, material is in wetting state；
3) add and bond dispersant, stirring causes material to be well mixed；
4) above-mentioned material obtains continuous dearsenic catalyst by extruded moulding, drying and roasting.
For in the preparation method of above-mentioned continuous dearsenic catalyst, in embodiments of the present invention, molecular screen primary powder is from big
The 13X type original powder in aperture, active component solution are 0.3mol/L copper nitrate or copper chloride solution.A certain amount of original is weighed first
Powder, stir while adding copper nitrate or copper chloride solution, for material in after wetting state, the aluminium glue for adding polymolecularity is molten
Liquid is made to bond dispersant, stirs always, is well mixed all materials and reaches extrusion state.By extruded moulding, drying and
After roasting, sign measurement is carried out to catalyst, its effective aperture is 0.8~1.5nm, is mainly distributed with micropore；It is 650 than surface
~720m2/g；Total pore volume is 0.34~0.39cm3More than 80%, the performance determines catalysis by/g, wherein micro pore volume accounting
Agent has preferably reaction than surface, and beneficial to the export of catalysate.
For in the preparation method of above-mentioned continuous dearsenic catalyst, further, can specifically use following preparation technology bar
Part is realized：
A) catalyst carrier is prepared using 13X types molecular screen primary powder, and its bulk density is 0.38g/ml, and pore size distribution is mainly
0.8~1.5nm, CO2Adsorbance be 22.5ml/g.
B) catalyst activity component matches：Match and calculate by the aqueous solution, Cu2+Concentration be 0.3M, 1Kg molecular screen primary powders,
Need the Cu (NO for adding 0.5L3)2Solution, stirred during addition in solubilization liquid.
C) in catalyst preparation process in order to increase the scattered and shaping strength of mantoquita, it is necessary to which the aluminium for adding polymolecularity is molten
Glue, 1Kg molecular screen primary powders about need to add 0.2L Alumina gel.
D) shaping of catalyst：After active component is added in molecular screen primary powder and bonds dispersant, extruded moulding is carried out；
E) 3h is dried at 120 DEG C first after shaping of catalyst, then then at 250 DEG C of roasting 2h, is finally made qualified and urges
Agent.
Above-mentioned continuous dearsenic catalyst uses special process, the arsenic hydride in industrial tail gas can be continuously removed, without regeneration；
Arsenic hydride in tail gas can be removed to 0.1mg/m3Hereinafter, gas can meet to do the chemical industry of high added value carbon one after dearsenification
The requirement of product.This catalyst is mixed using solid powder with liquid agitation, no waste liquid, useless solid generation, industrial amplification production
Easily, process conditions control well.The applicable process condition range of catalyst provided by the invention is：
1) operating pressure of fixed bed catalyst is 1~5atm；
2) bed temperature of fixed bed catalytic reactor is 200~250 DEG C, and optimal reaction temperature is 220 DEG C；
3) reaction velocity is 3000~10000h-1, most preferably 5000h-1；
Compared with prior art, the beneficial effects of the invention are as follows：
The present invention provides a kind of continuous dearsenic catalyst for industrial tail gas purification and preparation method thereof, has following excellent
Point：
(1) this catalyst is using the arsenic hydride that can be continuously removed after special process in industrial tail gas, without regeneration.It can incite somebody to action
Arsenic hydride in tail gas is removed to 0.1mg/m3Hereinafter, gas can meet to do the chemical products of high added value carbon one after dearsenification
Requirement.
(2) this catalyst may be directly applied to yellow phosphoric tail gas atmosphere, and resistant to sulfur, resistance to phosphorus work well, also can directly applied
In calcium carbide tail gas, and do not reacted substantially with other impurities in running, be applicable to different industrial tail gas atmosphere and work
Skill flow.
(3) this catalyst preparation process is simple, and operation operation is easy, and it is low to prepare cost.
(4) this catalyst is mixed using solid powder with liquid agitation, no waste liquid, useless solid generation, industrial amplification production
Easily, process conditions control well.
(5) arsenic hydride in industrial tail gas is converted into dilute arsenic acid form and exported by this catalyst, is easy to collect, is not produced
Secondary pollution.
Brief description of the drawings
Fig. 1 is the FB(flow block) of preparation method in the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawings, the present invention, the model of but do not limit the invention in any way are further described by embodiment
Enclose.
The present invention provides a kind of continuous dearsenic catalyst for industrial tail gas purification, and the continuous dearsenic catalyst is self-control
The modified molecular sieve catalyst of shaping.Fig. 1 is the preparation technology FB(flow block) of continuous dearsenic catalyst of the invention.Wherein, molecule
The 13X type original powder that former powder selects large aperture is sieved, active component solution is 0.3mol/L copper nitrate or copper chloride solution.Claim first
A certain amount of former powder is measured, is stirred while adding copper nitrate or copper chloride solution, material adds high score in after wetting state
The aluminium glue solution for dissipating property is made to bond dispersant, stirs always, is well mixed all materials and reaches extrusion state.By extrusion
After shaping, drying and roasting, sign measurement is carried out to catalyst, its effective aperture is 0.8~1.5nm, is mainly distributed with micropore；
It is 650~720m than surface2/g；Total pore volume is 0.34~0.39cm3/ g, wherein micro pore volume accounting are more than 80%, the performance
Determine that catalyst has preferably reaction than surface, and beneficial to the export of catalysate.
Embodiment specifically realizes the preparation of above-mentioned continuous dearsenic catalyst using following preparation process condition：
A) catalyst carrier is prepared using 13X types molecular screen primary powder, and its bulk density is 0.38g/ml, and pore size distribution is mainly
0.8~1.5nm, CO2Adsorbance be 22.5ml/g.
B) catalyst activity component matches：Match and calculate by the aqueous solution, Cu2+Concentration be 0.3M, 1Kg molecular screen primary powders,
Need the Cu (NO3) for adding 0.5L2Solution, stirred during addition in solubilization liquid.
C) in catalyst preparation process in order to increase the scattered and shaping strength of mantoquita, it is necessary to which the aluminium for adding polymolecularity is molten
Glue, 1Kg molecular screen primary powders about need to add 0.2L Alumina gel.
D) shaping of catalyst：Extruded moulding is carried out after active component and scattered binding agent are added in molecular screen primary powder；
E) 3h is dried at 120 DEG C first after shaping of catalyst, then then at 250 DEG C of roasting 2h, is finally made qualified and urges
Agent.
Embodiment one：
Weigh 36.24g copper nitrates (Cu (NO3)2·3H2O) by its uniform dissolution, the 500ml aqueous solution is formulated as, to prevent
Copper nitrate hydrolyzes, and adds 5 drop nitric acid.1Kg 13X molecular screen primary powders are weighed, the solution configured and former powder are mixed, are
Help the Alumina gel of molecular sieve molded addition 0.2L high dispersives, and stir.Using banded extruder by material extruding.By bar
After shape thing dries in the shade, baking oven is put into 120 DEG C of baking 3h, roaster is then transferred to, with 250 DEG C of roasting 2h, finally obtains finished product dearsenification and urge
Agent.
By this Catalyst packing in fixed bed reactors.Temperature of reactor is set in 220 DEG C；Air speed is set in
10000h-1；Reaction pressure is normal pressure.Yellow phosphoric tail gas is prepared for laboratory simulation yellow phosphoric tail gas component, composition CO90%,
PH30.1%th, H2S0.3%, AsH3450mg/m3, other be N2.After the gas is passed through fixed bed reactors purification, the arsenic in tail gas
Content is reduced to 0.1mg/m3Hereinafter, the presence of other compositions such as sulphur, phosphorus does not influence dearsenification effect, condensation washing collection after purification
Thing is only dilute arsenic acid.Successive reaction 700h, catalytic activity are unchanged.
Embodiment two：
Weigh 51.15g copper chlorides (CuCl2·2H2O), by its uniform dissolution, it is formulated as the 1L aqueous solution；Weigh 2Kg 13X
Molecular screen primary powder, solution and its are stirred, 0.4L polymolecularity Alumina gel solution is added in whipping process, continues to stir
To uniform.Extruded moulding is carried out on banded extruder.After drying in the shade, 3h is dried under the conditions of 120 DEG C, then in 250 DEG C of roaster
2h is fired, obtains finished product dearsenic catalyst.
By the Catalyst packing of preparation in fixed bed reactors.Temperature of reactor is set in 200 DEG C；Air speed is set in
5000h-1；Reactor pressure position normal pressure.Calcium carbide tail gas gas is prepared in simulation, wherein arsenic content is 750mg/m before purification3.It is passed through
After fixed bed reactors purification, the arsenic content in exit gas is reduced to 0.1mg/m3Below.Condensation washing gleanings after purification
Only dilute arsenic acid.Successive reaction 1000h, catalytic activity are unchanged.
It should be noted that the purpose for publicizing and implementing example is that help further understands the present invention, but the skill of this area
Art personnel are appreciated that：Do not departing from the present invention and spirit and scope of the appended claims, various substitutions and modifications are all
It is possible.Therefore, the present invention should not be limited to embodiment disclosure of that, and the scope of protection of present invention is with claim
The scope that book defines is defined.
Claims (7)
1. a kind of continuous dearsenic catalyst for industrial tail gas purification, the continuous dearsenic catalyst by active component solution,
13X molecular screen primary powders are made with dispersant extruded moulding, drying and roasting is bonded；The active component is mantoquita；Institute
State the copper nitrate or copper chloride solution that active component solution is 0.3mol/L；The ratio surface of the molecular sieve is 650~720m2/
G, the effective aperture of molecular sieve is 0.8~1.5nm, and total pore volume is 0.34~0.39cm3/ g, wherein micro pore volume accounting exceed
80%；After strip is dried in the shade after extruded moulding, baking oven is put into 120 DEG C of baking 3h, roaster is then transferred to, with 250 DEG C of roastings
2h；The continuous dearsenic catalyst is continuously reacted by catalytic oxidation with the arsenic hydride in industrial tail gas, makes arsenic hydride
Hydration reaction occurs after being oxidized to arsenic trioxide or diarsenic pentoxide, then with arsenic acid or arsenious acid export bed, reaches company
The purpose of arsenic hydride in continuous purification gas phase.
2. continuous dearsenic catalyst as claimed in claim 1, it is characterized in that, the cohesive dispersant is Alumina gel solution.
3. continuous dearsenic catalyst as claimed in claim 1, it is characterized in that, the continuous dearsenic catalyst be used for yellow phosphoric tail gas and
Calcium carbide stove exhaust atmosphere.
4. continuous dearsenic catalyst as claimed in claim 3, it is characterized in that, the active component of the continuous dearsenic catalyst is in urging
There is no significant change before and after oxidation.
5. the preparation method of continuous dearsenic catalyst, comprises the following steps described in claim 1：
1) active component solution is configured, the active component is mantoquita；
2) molecular screen primary powder is weighed, the step 1) active component solution is added into molecular screen primary powder, material is in wetting
State；
3) add and bond dispersant, stirring causes material to be well mixed；
4) step 3) the well mixed material obtains continuous dearsenic catalyst by extruded moulding, drying and roasting.
6. the preparation method of continuous dearsenic catalyst as claimed in claim 5, it is characterized in that, the step 2) molecular screen primary powder is
The 13X type original powder of large aperture.
7. the preparation method of continuous dearsenic catalyst as claimed in claim 5, it is characterized in that, the step 3) bonding that adds is disperseed
Agent is specially to add about 0.2L Alumina gel solution per 1Kg molecular screen primary powders.
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| CN109589762B (en) * | 2018-12-29 | 2021-09-10 | 沈阳三聚凯特催化剂有限公司 | Gas-phase dearsenic agent and preparation method thereof |
| CN110449121A (en) * | 2019-08-07 | 2019-11-15 | 中国船舶重工集团公司第七一八研究所 | A kind of adsorbent and preparation method thereof of high-efficient purification hydride gas |
| CN110639466B (en) * | 2019-09-30 | 2020-12-01 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
| CN111672533B (en) * | 2020-06-28 | 2021-07-13 | 北京化工大学 | Dearsenifying catalyst and its prepn |
| CN112844006A (en) * | 2020-12-28 | 2021-05-28 | 马边长和电力有限责任公司 | Yellow phosphorus tail gas purification method |
| CN112755957B (en) * | 2021-01-12 | 2022-04-15 | 武汉科林化工集团有限公司 | High-efficiency dearsenic agent and preparation method thereof |
| CN115869912A (en) * | 2023-02-15 | 2023-03-31 | 格林斯达(北京)环保科技股份有限公司 | Purifying material for waste gas containing hydride |
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| CN103566947B (en) * | 2012-08-07 | 2016-01-20 | 北京三聚环保新材料股份有限公司 | A kind of arsenic removal catalyst and preparation method thereof |
| CN103055833B (en) * | 2013-01-15 | 2015-06-24 | 苏州工业园区安泽汶环保技术有限公司 | Preparation method of ammonia removal material |
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| CN101831319A (en) * | 2010-05-13 | 2010-09-15 | 中国石油大学(北京) | Purification process for preparing C4 materials for isobutene by C4 linear chain olefin skeleton isomerism |
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