CN105879662A - Method for purifying arsenic hydride gas in industrial waste gas - Google Patents

Abstract

The invention relates to a method for purifying arsenic hydride gas in industrial waste gas. The method comprises the steps: firstly, preparing a cobalt phthalocyanine solution and a mixed modified solution of one or more ions of Fe<3+>, Mn<2+> and Ni<2+>, putting molecular sieve into the modified solution, dipping, drying, and roasting to obtain a molecular sieve modified catalyst; putting the modified molecular sieve catalyst into a fixed bed reactor, carrying out solid catalytic oxidation purification of the industrial waste gas with the CO volume fraction of 80-90 %, the O2 volume fraction of less than 2% and the AsH3 concentration of 500-1600 mg/m<3>, and reducing the content of arsenic hydride to 0.3 mg/m<3> or less. The modified molecular sieve catalyst has high low-temperature activity, can be used in a complex industrial gas atmosphere containing CO, H2S, SO2, COS, PH3 and the like, and has good selectivity for AsH3; and the method can be applied in large coking plants, yellow phosphorus production plants, calcium carbide plants and other plants, and puts forward a feasible way for Chinese air pollution control and monocarbon chemical engineering process development.

Description

A kind of method of purifying arsenic hydride gas in industrial waste gas

Technical field

A kind of method that the present invention relates to purifying arsenic hydride gas in industrial waste gas, belongs to waste gas pollution control and treatment Chemical Engineering Technology Field.

Background technology

Arsenic hydride is colourless gas, belongs to hypertoxic type material, its toxicity big 7 times than lewisite, compares cacodyl Big 400 times of natrium arsenicum.In commercial production, when smelting containing arsenic ferrosilicon and storage, contact humid air or use water The slag of the red-hot arsenic-containing ores of quenching can produce arsenic hydride；Carbide manufacture, the production of acetylene and use, metal system The occasions such as the acid of product is watered, accumulator charging, production synthetic dyestuffs, all can produce arsenic hydride.Especially raw at carbide In product, the calcium carbide furnace gas often producing the generation of 1t carbide is about 400m³, consisting of: CO:80%～90%； CO₂: 0.2%～5%；N₂: 1%～2%；O₂: less than 2%；AsH₃: 500～1500mg/m³Little with concentration In 300mg/m³In sulfur, phosphorus impurities gas, particularly tail gas, the existence of the major impurity such as arsenic limits in tail gas CO uses as high-quality Organic Chemicals gas.Therefore, highly purified CO gas, purified treatment carbide to be obtained The materials such as the arsenic hydride in furnace exhaust gas are crucial.This is to utilizing calcium carbide stove exhaust as producing C1 chemical industry product Raw material, exploitation deep processed product and sustainable development are significant.Additionally China (TJ36-79) workshop is empty In gas, arsenic hydride maximum permissible concentration is 0.3mg/m³, therefore purifying arsenic hydride also becomes protection health, disappears A kind of necessary means except air pollution.

Publication No. CN1076173 discloses a kind of purification PH₃And AsH₃Immesion active carbon, be used for purifying PH in hydrogen stream₃And AsH₃.The method Immesion active carbon is with ature of coal granular active carbon as carrier, its dipping Component has Cu, Hg, Cr, Ag.Its Immesion active carbon preparation method is as follows: sieve takes the ature of coal of certain particle size Grain activated carbon, uses CuSO₄、Cr₂O₃NH₄OH solution and AgNO₃Ethanol solution be sufficiently mixed, at 40-60 HgCl is added at DEG C₂, by the 70-80% liquid impregnation of activated carbon water capacity, the pH of impregnation liquid is 8-13, leaching Placing more than 3 hours after stain, said process is repeated twice, obtains Immesion active carbon.The method is to arsenic The clean-up effect of hydrogen can reach international safe level 0.05PPm.

Publication No. CN101219388 discloses a kind of dearsenization of arsenic hydride removing in phosphine gas Agent FeCuP alloy and the application in dearsenization thereof.Hydrodearsenic Catalyst is the FeCuP alloy prepared by oxidation-reduction method. This alloy Cu content mass percent is 20%-35%, and P content mass percent is 0.9%-6.0%, its Yu Weitie.Dearsenization step: be passed through nitrogen in airtight gas circuit and get rid of air, heat dearsenization reactor, arsenic will be contained The phosphine gas changing hydrogen is passed through equipped with carrying out dearsenization in the reactor of Hydrodearsenic Catalyst, gas after dearsenization import equipped with In the centrifuge tube of silver salt absorbing liquid, after 45min, take off centrifuge tube, add chloroform and supply 4mL, use 1cm ratio Colour tube, measures absorbance A at 520nm wavelength.Carry out blank experiment and control experiment simultaneously, calculate dearsenization Rate.The method dearsenization temperature arsenic-removing rate when 100 DEG C is 80.53%, and temperature arsenic-removing rate when 120 DEG C is 93.34 %, temperature arsenic-removing rate when 175 DEG C is 100%.

Existing method there is problems in that (1) is only limitted to PH in air₃And AsH₃Or PH in hydrogen stream₃And AsH₃ Removing, be not directed to AsH under the reducing atmosphere of the industrial tail gas containing CO₃Removing；(2) it is all to be only limitted to together Time remove both toxic and harmfuls, mixed-gas atmosphere is the most single；(3) the regeneration situation of Hydrodearsenic Catalyst is also Undeclared, if Hydrodearsenic Catalyst cannot regenerate or regenerability is relatively low, then easily cause secondary pollution and increase cost.

For the problems referred to above, the present invention propose modified molecular screen Gas-solid phase catalyzing, oxidizing and purifying containing a large amount of CO and O₂Volumn concentration is less than the arsenic hydride in the industrial waste gas of 2%, by the AsH in industrial gases₃It is down to 0.3mg/m³Below.For China's air pollution control and C1 chemical industry process exploitation, one feasible way is proposed.

Summary of the invention

The present invention provides a kind of method of purifying arsenic hydride gas in industrial waste gas, using molecular sieve modified rear as urging Agent, solid catalysis oxidation, purification contains a large amount of CO and O₂Volumn concentration is less than in the industrial waste gas of 2% Arsenic hydride, by AsH therein₃It is down to 0.3mg/m³Below.

The present invention completes according to the following steps:

1). prepared by catalyst: preparation mass percent is the Cobalt Phthalocyanine solution of 0.01%～0.1%, in room temperature Lower stirring, adds the Fe of 0.5～2mol/L while stirring³⁺The Mn of solution, 0.2～1mol/L²⁺Solution and The Ni of 0.1～0.5mol/L²⁺One or more in solution, the most at room temperature continue stirring 0.5h, obtain Cobalt Phthalocyanine and Fe³⁺、Mn²⁺、Ni²⁺In the mixed and modified solution of one or more ions, described Cobalt Phthalocyanine is molten Liquid and Fe³⁺Liquor capacity ratio is 20～100: 1, Cobalt Phthalocyanine solution and Mn²⁺Liquor capacity ratio 20～50: 1；Phthalein Cyanines cobalt liquor and Ni²⁺Liquor capacity ratio 100～500: 1；The modification liquid obtained at room temperature is aged 24h be allowed to Obtain modification liquid completely after mixing, molecular sieve is put in this modification liquid, stir in the constant temperature waters of 20～40 DEG C Mix 1h, after stirring, at room temperature impregnate 48h, be then passed through filter, before filtering residue is modified molecular sieve catalyst Drive body, it is dried at a temperature of 90～120 DEG C 24h, is finally putting in roaster, and at the bar of anaerobic Under part, the temperature calcination 12h with 200～350 DEG C obtains modified molecular sieve catalyst.

2). purification process: modified molecular sieve catalyst prepared more than adding in fixed bed reactors, add Thermosetting fixed bed reactor to 50～90 DEG C, by content be CO volumn concentration be 80%～90%, H₂S is dense Degree is 100～200mg/m³, SO₂10～100mg/m³, COS 100～200mg/m³, PH₃100～150mg/m³, AsH₃500～1600mg/m³, oxygen volumn concentration be 0.2%～2% industrial waste gas be passed through fixing Bed reactor carries out adsorption cleaning reaction, measures reactor outlet AsH₃The concentration of gas is 0.3mg/m³Below.

3). the catalyzer with water steam washing 3～6h that catalyst regeneration process flow process inactivates after purifying, then Being dried 12h at a temperature of 100～150 DEG C and just can obtain regenerated catalyst, catalyst regeneration efficiency is more than 90 %.

The invention have the advantage that (1) modified molecular sieve catalyst can in large-scale coke-oven plant, phosphorus production factory, electricity Shi Changdeng producer extensively applies, and has low temperature active high, can be containing CO, H₂S、SO₂、COS、PH₃Deng Complex industrial gas atmosphere uses, removes AsH therein₃, there is anti-poisonous impurities interference characteristic, and right AsH₃There is good selectivity；(2) catalyst can use under conditions of oxygen volumn concentration≤2%；(3) Using molecular sieve is that the catalyst cost prepared by support modification is relatively low, and removing performance is high, and catalyst is renewable, Still preferable catalytic performance is possessed after regeneration.

Detailed description of the invention

Embodiment one: by the Cobalt Phthalocyanine solution that mass percent is 0.01%, be stirred at room temperature mixing, stir Adding concentration while mixing is the MnSO of 0.2mol/L₄Solution, its Cobalt Phthalocyanine solution and MnSO₄The volume of solution Ratio is 20: 1, the most at room temperature continues stirring 0.5h, obtains Cobalt Phthalocyanine, Mn²⁺The mixed and modified solution of ion, After the modification liquid obtained at room temperature is aged 24h, X-type molecular sieve is put in this modification liquid, then exist The constant temperature waters of 20 DEG C is stirred 1h, after stirring, at room temperature impregnates 48h, through filtering after dipping, at 90 DEG C Baking temperature under be dried 24h, be finally putting in roaster, and with the temperature of 250 DEG C under conditions of anoxybiotic Roasting 12h can purify modified molecular sieve catalyst used.Modified molecular sieve catalyst specific surface area up to 323m²/g。

With the modified molecular sieve catalyst prepared in above-mentioned condition in fixed bed reactors, constant with 60 DEG C Temperature, is passed through to be clean containing CO:80%, H₂S:150mg/m³、SO₂: 30mg/m³, COS:150mg/m³、 PH₃: 130mg/m³Closed electric furnace tail gas, wherein arsine gas concentration is 1500mg/m³, reaction velocity is 800/h, with band TCD and the gas chromatograph for determination of PFD detector, after adsorption cleaning, arsine gas exists Within 30h, exit concentration is less than 0.3mg/m³, adsorption capacity is up to 12.2mg/g.

By the catalyzer with water steam washing 3h after inactivation, at a temperature of 110 DEG C, then it is dried 12h just can obtain Regenerated catalyst, catalyst revival reaches 96%, i.e. adsorption capacity is the 96% of fresh catalyst.

Embodiment two: by the Cobalt Phthalocyanine solution that mass percent is 0.1%, be stirred at room temperature mixing, stirring While add concentration be the FeCl of 1mol/L₃Solution, its Cobalt Phthalocyanine solution and FeCl₃The volume ratio of solution is 30: 1, the most at room temperature continue stirring 0.5h, obtain Cobalt Phthalocyanine, Fe³⁺The mixed and modified solution of ion, will After the modification liquid obtained at room temperature is aged 24h, Y type molecular sieve is put in this modification liquid, then 40 DEG C constant temperature waters in stir 1h, at room temperature impregnate 48h after stirring, after dipping through filter, at 100 DEG C It is dried 24h under baking temperature, is finally putting in roaster, and with the temperature roasting of 300 DEG C under conditions of anoxybiotic Burn 12h and can purify modified molecular sieve catalyst used.Modified molecular sieve catalyst specific surface area up to 528m²/g。

With the modified molecular sieve catalyst prepared in above-mentioned condition in fixed bed reactors, constant with 80 DEG C Temperature, is passed through to be clean containing CO:85%, H₂S:120mg/m³、SO₂: 15mg/m³, COS:100mg/m³、 PH₃: 110mg/m³Closed electric furnace tail gas, wherein arsine gas concentration is 800mg/m³, reaction velocity is 1500/h, after adsorption cleaning, arsine gas exit concentration within 36h is less than 0.3mg/m³, adsorption capacity For 11.5mg/g.

By the catalyzer with water steam washing 4h after inactivation, at a temperature of 130 DEG C, then it is dried 12h just can obtain Regenerated catalyst, catalyst revival reaches 95%, i.e. adsorption capacity is the 95% of fresh catalyst.

Embodiment three: by the Cobalt Phthalocyanine solution that mass percent is 0.1%, be stirred at room temperature mixing, stirring While add the FeCl of 2mol/L₃Solution, the MnSO of 1mol/L₄Solution and the NiCl of 0.5mol/L₂Molten Liquid, its Cobalt Phthalocyanine solution and FeCl₃、MnSO₄Solution, NiCl₂The volume ratio of solution is respectively 50: Isosorbide-5-Nitrae 0: 1, 200: 1, the most at room temperature continue stirring 0.5h, obtain Cobalt Phthalocyanine, Fe³⁺、Mn²⁺、Ni²⁺The mixing of ion Modified solution, after at room temperature the modification liquid obtained is aged 24h, puts in this modification liquid by X-type molecular sieve, Then in the constant temperature waters of 30 DEG C, stir 1h, after stirring, at room temperature impregnate 48h, through filtering after dipping, Under the baking temperature of 120 DEG C, it is dried 24h, is finally putting in roaster, and with 350 under conditions of anoxybiotic DEG C temperature calcination 12h can purify modified molecular sieve catalyst used.Modified molecular sieve catalyst specific surface area Up to 356m²/g。

With the modified molecular sieve catalyst prepared in above-mentioned condition in fixed bed reactors, constant with 90 DEG C Temperature, is passed through to be clean containing CO:90%, H₂S:200mg/m³、SO₂: 30mg/m³, COS:200mg/m³、 PH₃: 150mg/m³Closed electric furnace tail gas, wherein arsine gas concentration is 1600mg/m³, reaction velocity is 2000/h, after adsorption cleaning, arsine gas concentration within 48h is less than 0.3mg/m³, adsorption capacity up to 14mg/g。

By the catalyzer with water steam washing 6h after inactivation, at a temperature of 150 DEG C, then it is dried 12h just can obtain Regenerated catalyst, catalyst revival reaches 98%, i.e. adsorption capacity is the 98% of fresh catalyst.

Claims (3)

1. the method for a purifying arsenic hydride gas in industrial waste gas, it is characterised in that: it completes according to the following steps,

1). prepared by catalyst: preparation mass percent is the Cobalt Phthalocyanine solution of 0.01%～0.1%, in room temperature Lower stirring, adds the Fe of 0.5～2mol/L while stirring³⁺The Mn of solution, 0.2～1mol/L²⁺Solution and The Ni of 0.1～0.5mol/L²⁺One or more in solution, the most at room temperature continue stirring 0.5h, obtain Cobalt Phthalocyanine and Fe³⁺、Mn²⁺、Ni²⁺In the mixed and modified solution of one or more ions, described Cobalt Phthalocyanine is molten Liquid and Fe³⁺Liquor capacity ratio is 20～100: 1, Cobalt Phthalocyanine solution and Mn²⁺Liquor capacity ratio 20～50: 1, Cobalt Phthalocyanine solution and Ni²⁺Liquor capacity ratio 100～500: 1, by the oldest for the mixed and modified solution obtained Change after 24h is allowed to mixing and obtain modification liquid, molecular sieve is put in this modification liquid, at the thermostatted water of 20～40 DEG C Territory is stirred 1h, after stirring, at room temperature impregnates 48h, be then passed through filter, before obtaining modified molecular sieve catalyst Drive body, it is dried at a temperature of 90～120 DEG C 24h, is finally putting in roaster, and at the bar of anaerobic Under part, the temperature calcination 12h with 200～350 DEG C obtains modified molecular sieve catalyst；

2). purification process: modified molecular sieve catalyst prepared more than adding in fixed bed reactors, add Industrial waste gas, to 50～90 DEG C, is passed through fixed bed reactors and carries out adsorption cleaning reaction by thermosetting fixed bed reactor, Measure reactor outlet AsH₃The concentration of gas is 0.3mg/m³Hereinafter, the modified molecular sieve catalyst after inactivation Carry out Regeneration Treatment.

The method of purifying arsenic hydride gas in industrial waste gas the most according to claim 1, it is characterised in that: It is with steam, it to be rinsed 3-6h, then that modified molecular sieve catalyst after described inactivation carries out Regeneration Treatment 12h it is dried at a temperature of 100-150 DEG C.

The method of purifying arsenic hydride gas in industrial waste gas the most according to claim 1, it is characterised in that: The component content of described industrial waste gas be CO volumn concentration be 80%～90%, H₂S concentration be 100～ 200mg/m³, SO₂10～100mg/m³, COS 100～200mg/m³, PH₃100～150mg/m³, AsH₃500～ 1600mg/m³, oxygen volumn concentration is 0.2～2%.