CN103551030B - A kind ofly remove cleanser of phosphorus arsenic in calcium carbide stove exhaust and its preparation method and application - Google Patents
A kind ofly remove cleanser of phosphorus arsenic in calcium carbide stove exhaust and its preparation method and application Download PDFInfo
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- CN103551030B CN103551030B CN201310527439.5A CN201310527439A CN103551030B CN 103551030 B CN103551030 B CN 103551030B CN 201310527439 A CN201310527439 A CN 201310527439A CN 103551030 B CN103551030 B CN 103551030B
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Abstract
The invention discloses a kind of cleanser removing phosphorus arsenic in calcium carbide stove exhaust, with A-X combined zeolite for carrier, load removes the active metal component of phosphorus arsenic, prepares by kneading method.Compared with prior art, cleanser of the present invention is with metals such as copper, molybdenum, iron, zinc for active component, and using A-X combined zeolite as carrier, the adsorption layer pore-size distribution making cleanser is more extensive, has good assimilation effect to the phosphorus of different pore size, arsenide.Cleanser efficient quick of the present invention, just can realize effective removal of phosphide and the contour polluter of arsenide in calcium carbide stove exhaust at normal temperatures simultaneously, after purification in calcium carbide stove exhaust phosphorus and arsenic content all≤0.1mg/Nm
3, the recycling of carbon monoxide can be met completely.
Description
Technical field
The present invention relates to the cleanser for purifying calcium carbide furnace tail gas, especially a kind ofly remove cleanser of phosphorus arsenic in calcium carbide stove exhaust and its preparation method and application.
Background technology
Calcium carbide is the important base stock of organic synthesis industry, is that raw material can produce polyvinyl chloride, neoprene, polyvinyl alcohol, acetylene carbon black, trichloro-ethylene etc., also makes the desulfurizing agent of iron and steel, also for Metal Cutting and welding gas with carbide acetylene.Polyvinyl chloride (PVC) industry is the major consumers field of domestic calcium carbide, accounts for 75% of calcium carbide consumption.China is first calcium carbide producing country in the world, family more than 450 of total calcium carbide manufacturing enterprise, calcium carbide production capacity 2,200 ten thousand tons in 2010, output 1,500 ten thousand tons.
It is traditional high pollution, high energy consumption industry that calcium carbide is produced.Closed type calcium carbide furnace is often produced one ton of calcium carbide by-product calcium carbide stove exhaust and is about 400Nm
3.CO, sulfide, fluoride, the contour polluter of chloride is comprised in calcium carbide stove exhaust.Only by closed calcium carbide output 1,000 ten thousand tons, raw calcium carbide stove exhaust 4,000,000,000 Nm of the annual common property of China
3above, the Toxic such as 6000 tons of tar, 1810 tons of fluorides, 6500 tons of sulfide is had to enter air.According to Cress technology, tar, fluorine, sulphur refuse can utilize in harmless process, the CO resource of annual recoverable, amount to standard coal more than 2,090,000 tons, reduce discharging 2,000,000 tons of CO
2.
Calcium carbide stove exhaust composition is very complicated, must to its purification in addition before comprehensive utilization, but purification techniques difficulty is very large, there is no maturation, advanced feasible industrialization clearer production technology and equipment both at home and abroad at present, therefore recovery utilization rate is very low, mostly directly emptying or light discharge, and small part is used as the fuel of waste heat boiler, cause serious atmosphere pollution, cause again the huge wasting of resources simultaneously.To the end of the year 2011, national calcium carbide stove exhaust utilization will be less than 5 billion cubic meters, and utilization rate is less than 10%.Therefore, exploitation is advanced, calcium carbide stove exhaust purification clean technologies are extremely urgent reliably.
At present, the phosphorus arsenic in calcium carbide stove exhaust mainly contains wet method and dry technique technique.Have hypertoxic waste water that is phosphorous, arsenic after Wet technique washing to produce, very big pollution is caused to environment.Dry technique utilizes chemisorbed principle, adopts active metal to remove impurity, but common cleanser is difficult to remove clean by phosphorus and arsenic simultaneously, needs substep to remove.
Summary of the invention
Given this, the object of this invention is to provide a kind of simple, cleanser of effectively removing phosphide in calcium carbide stove exhaust and arsenide efficiently, produce secondary pollution, the defect very large to ambient influnence to overcome in existing minimizing technology clean-up effect difference or complex process, purification process.
Another object of the present invention is to provide the preparation method of above-mentioned cleanser.
Another object of the present invention is to provide the application of above-mentioned cleanser.
Remove a cleanser for phosphorus arsenic in calcium carbide stove exhaust, with A-X combined zeolite for carrier, load removes the active metal component of phosphorus arsenic, and to account for the mass percent of cleanser, load capacity is preferably 1%-40%, more preferably 5%-30%.
Preferably, active metal component is two or more in molybdenum, copper, iron, zinc etc.
Preferably, A-X combined zeolite is made up of the Wessalith CS of 15%-65% weight and the X zeolite of 35%-85% weight, preferred, and A-X combined zeolite is made up of the Wessalith CS of 25%-55% weight and the X zeolite of 45%-75% weight.
According to sial atomic ratio, X zeolite be divided into low-silica X zeolite, in silicon X-shaped zeolite and the silicon X-shaped zeolite of height, wherein, Si/Al atomic ratio is called low-silica X zeolite lower than 1.1, Si/Al atomic ratio is silicon X-shaped zeolite in being called of 1.1-1.2 scope, Si/Al atomic ratio higher than 1.2 be called high silicon X-shaped zeolite.
Applicant through experiment prove, in A-X combined zeolite, low-silica X zeolite as carrier for remove phosphorus in calcium carbide stove exhaust, arsenic effect better.
The Si/Al atomic ratio of X zeolite is preferably 0.90-1.2, more preferably 1-1.1.
Prepare the above-mentioned method removing the cleanser of phosphorus arsenic in calcium carbide stove exhaust, comprising:
(1) under room temperature, fully stirring condition, SiO is pressed
2/ Al
2o
3sodium silicate aqueous solution adds rapidly in sodium aluminate aqueous solution by the preferred 1.8-2.5 of mol ratio 1.2-3.6, form gel, stir 1 hour-2 hours, move in stainless steel crystallizer, leave standstill aging 2 hours-4 hours, alternating temperature crystallization is carried out at 40 DEG C-110 DEG C, the temperature controlling alternating temperature crystallization comprises more than 70 DEG C temperature and less than 70 DEG C temperature, within 30 hours-80 hours, post crystallization completes, filter, solid is spent deionized water three times, 90 DEG C of-110 DEG C of dryings, obtain the combined zeolite powder of A-X intersection symbiosis;
(2) two or more in zeolite powder, the sesbania powder accounting for the mass percent 1%-15% of cleanser and copper sulphate obtained in step (1), nitric acid molybdenum, ferric nitrate, zinc nitrate and water are mixed, extrusion, at 400 DEG C-700 DEG C, roasting 2 hours-4 hours, to obtain final product.
Under normal circumstances, the generation of type A zeolite can be promoted under higher temperature is as more than 70 DEG C conditions.Therefore, in order to obtain the combined zeolite powder of A-X intersection symbiosis, the alternating temperature crystallization process of step (1) needs that partial routine carries out more than 70 DEG C and partial routine carries out below 70 DEG C, can be controlled the relative quantity of A type crystalline element in product and X-type crystalline element by crystallization control temperature.
Preferred further, in order to obtain more low-silica X zeolite, at least part of crystallization process needs to control to carry out below 60 DEG C.
Preferably, the alternating temperature crystallization range of above-mentioned steps (1) is 55 DEG C-95 DEG C.
Above-mentioned cleanser is used for removing phosphorus and arsenic in calcium carbide stove exhaust, gets rid of phosphorus in calcium carbide stove exhaust and arsenic, phosphorus and arsenic content can be removed to≤0.1mg/Nm under normal temperature condition by chemisorbed
3.
Research shows, the cleanser of supported copper, molybdenum, iron, zinc isoreactivity metal has good removal effect to phosphorus and arsenide, and the carrier of cleanser can be selected from active carbon or aluminium oxide or zeolite molecular sieve.Due to the complicated component of calcium carbide stove exhaust impurity, kind is different, also has nothing in common with each other to the requirement of carrier.Especially use zeolite as all the more so during cleanser carrier.Applicant finds through great many of experiments, Wessalith CS carrier removes better to the less phosphide of molecular diameter, and the removal effect of X zeolite carrier to the larger arsenide of molecular diameter is better, makes carrier with single Wessalith CS or X zeolite and be difficult to phosphide in calcium carbide stove exhaust and arsenide to remove totally simultaneously.The present invention with A-X combined zeolite for carrier, two or more component in a certain amount of copper of load, molybdenum, iron, zinc isoreactivity metal, kneading method is adopted to prepare the cleanser of calcium carbide stove exhaust dephosphorization and arsenic, prepare functional, constitutionally stable cleanser, achieve effective removal of phosphide and the contour polluter of arsenide in calcium carbide stove exhaust.
Compared with prior art, cleanser of the present invention with metals such as copper, molybdenum, iron, zinc for active component, using A-X combined zeolite as carrier, make the adsorption layer pore-size distribution of cleanser more extensive, good assimilation effect is had to the phosphorus of different pore size, arsenide, just can realize effectively removing of phosphorus and arsenide at normal temperatures simultaneously, after purification in tail gas phosphorus and arsenic content all≤0.1mg/Nm
3, the recycling of carbon monoxide can be met completely.
Detailed description of the invention
All features disclosed in this description, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can combine by any way.
Arbitrary feature disclosed in this description (comprising any accessory claim, summary), unless specifically stated otherwise, all can be replaced by other equivalences or the alternative features with similar object.That is, unless specifically stated otherwise, each feature is an example in a series of equivalence or similar characteristics.
Embodiment 1 prepares cleanser I
(1) 600 grams of sodium metasilicate (SiO are taken
2content 27.1wt%) be dissolved in 2400 ml deionized water, under room temperature, fully stirring condition, add 570 grams of sodium aluminate (Al
2o
3content 19.3wt%), make SiO in this reaction raw materials
2/ Al
2o
3mol ratio is 2.5:1, and gained gel stirs 1 hour, then moves in 1 liter of stainless steel crystallizer, and leave standstill aging 2 hours-4 hours, warming-in-water to 55 DEG C, crystallization is warming-in-water to 95 DEG C after 40 hours, and crystallization completes reaction in 10 hours.Filter, solid washs three times by 600 ml deionized water respectively, 90 DEG C of dryings, obtains the combined zeolite powder of A-X intersection symbiosis.
X-ray diffraction is analyzed (XRD analysis) and is shown, containing the type A zeolite of 30% and the X-type zeolite of 68% in combined zeolite, and Si/Al mol ratio 1.07:1.
(2) by the zeolite powder in step 1 65 grams, 7g sesbania powder, 12 grams of cupric sulfate pentahydrates, 18 gram of five water nitric acid molybdenum and 12 milliliters of aqueous solution, extrusion, at 500 DEG C, roasting 4 hours, is purified agent I.
The Contrast on effect embodiment of embodiment 2 three kinds of cleansers
Utilize the preparation method of embodiment 1, adopt the A-X combined zeolite powder that commercially available type A zeolite replacement step (1) obtains, prepare cleanser II, the A-X combined zeolite powder adopting commercially available low-silica X zeolite (Si/Al atomic ratio 1.03) replacement step (1) to obtain, prepares cleanser III.
Three kinds of cleansers are loaded in fixed adsorption bed respectively, investigate their removal effects to phosphide and arsenide impurity.
Table 1 unstripped gas forms
Operating condition: DN25 reaction tube, void tower linear speed: 0.05m/s, the time of staying: 20s, operating temperature: 25 DEG C, operating pressure: 0.5MPa, result is as follows:
Table 2 cleanser I is to the absorption result of phosphorus, arsenic impurities
Table 3 cleanser II is to the absorption result of phosphorus, arsenic impurities
Table 4 cleanser III is to the absorption result of phosphorus, arsenic impurities
From the result of table 2-4, compare with the cleanser (cleanser III) of single low-silica X zeolite as carrier with the cleanser (cleanser II) of single type A zeolite as carrier, can realize good removal effect as the cleanser of carrier to the phosphide in calcium carbide stove exhaust and arsenide by A-X combined zeolite, be a kind of desirable cleanser.
The present invention is not limited to aforesaid detailed description of the invention.The present invention expands to any new feature of disclosing in this manual or any combination newly, and the step of the arbitrary new method disclosed or process or any combination newly.
Claims (8)
1. remove a cleanser for phosphorus arsenic in calcium carbide stove exhaust, it is characterized in that, with A-X combined zeolite for carrier, load removes the active metal component of phosphorus arsenic; Described active metal component is two or more in molybdenum, copper, iron, zinc; To account for the mass percent of cleanser, the load capacity of active metal component is 1%-40%; Described A-X combined zeolite is made up of the Wessalith CS of 15%-65% weight and the X zeolite of 35%-85% weight.
2. remove the cleanser of phosphorus arsenic in calcium carbide stove exhaust as claimed in claim 1, it is characterized in that, the Si/Al atomic ratio of described X zeolite is 0.90-1.2.
3. remove the cleanser of phosphorus arsenic in calcium carbide stove exhaust as claimed in claim 2, it is characterized in that, the Si/Al atomic ratio of described X zeolite is 1-1.1.
4. prepare the method removing the cleanser of phosphorus arsenic in calcium carbide stove exhaust according to any one of claim 1-3, it is characterized in that, comprising:
(1) under room temperature, fully stirring condition, SiO is pressed
2/ Al
2o
3mol ratio 1.2-3.6, adds sodium silicate aqueous solution rapidly in sodium aluminate aqueous solution, forms gel, stir 1 hour-2 hours, move in stainless steel crystallizer, leave standstill aging 2 hours-4 hours, carry out alternating temperature crystallization at 40 DEG C-110 DEG C, the temperature controlling alternating temperature crystallization comprises more than 70 DEG C temperature and less than 70 DEG C temperature, within 30-80 hour, post crystallization completes, and filter, solid spends deionized water three times, 90 DEG C of-110 DEG C of dryings, obtain the combined zeolite powder of A-X intersection symbiosis;
(2) two or more in the zeolite powder in step 1, the sesbania powder accounting for the mass percent 1%-15% of cleanser and copper sulphate, nitric acid molybdenum, ferric nitrate, zinc nitrate and water are mixed, extrusion, at 400 DEG C-700 DEG C, roasting 2-4 hour, to obtain final product.
5. preparation method as claimed in claim 4, it is characterized in that, described crystallization process part is carried out below 60 DEG C.
6. preparation method as claimed in claim 4, it is characterized in that, the crystallization temperature of described step (1) is 55 DEG C-95 DEG C.
7. preparation method as claimed in claim 4, is characterized in that, described SiO
2/ Al
2o
3mol ratio is 1.8-2.5.
8. an application for the cleanser according to any one of claim 1-3, is characterized in that, the phosphorus of calcium carbide stove exhaust and arsenic content are removed to≤0.1mg/Nm by described cleanser
3.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076173A (en) * | 1993-02-20 | 1993-09-15 | 中国人民解放军防化研究院 | The Immesion active carbon of purifying hydrogen phosphide, hydrogen arsenide in the hydrogen stream |
| CN1341474A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp.-change adsorptive process |
| CN101219388A (en) * | 2008-01-11 | 2008-07-16 | 南开大学 | Dearsenifying agent FeCuP alloy for removing arsenic hydride in phosphoretted hydrogen gas and uses thereof |
| CN101402020A (en) * | 2008-10-30 | 2009-04-08 | 昆明理工大学 | Method for purifying arsenic hydride gas in industrial waste gas |
-
2013
- 2013-10-31 CN CN201310527439.5A patent/CN103551030B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1076173A (en) * | 1993-02-20 | 1993-09-15 | 中国人民解放军防化研究院 | The Immesion active carbon of purifying hydrogen phosphide, hydrogen arsenide in the hydrogen stream |
| CN1341474A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp.-change adsorptive process |
| CN101219388A (en) * | 2008-01-11 | 2008-07-16 | 南开大学 | Dearsenifying agent FeCuP alloy for removing arsenic hydride in phosphoretted hydrogen gas and uses thereof |
| CN101402020A (en) * | 2008-10-30 | 2009-04-08 | 昆明理工大学 | Method for purifying arsenic hydride gas in industrial waste gas |
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