CN103551105A - Calcium carbide furnace exhaust purifying agent, and preparation method and application thereof - Google Patents
Calcium carbide furnace exhaust purifying agent, and preparation method and application thereof Download PDFInfo
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- CN103551105A CN103551105A CN201310527354.7A CN201310527354A CN103551105A CN 103551105 A CN103551105 A CN 103551105A CN 201310527354 A CN201310527354 A CN 201310527354A CN 103551105 A CN103551105 A CN 103551105A
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Abstract
The invention discloses a calcium carbide furnace exhaust purifying agent, which can be prepared by processes of taking A-X combined zeolite as a vector and loading an active metal component by a kneading method. The purifying agent can be used for removing sulphur, phosphorus, arsenic, fluorine and chlorine of calcium carbide furnace exhaust under the condition of 60-280 DEG C, so that the content of each of the sulphur, the phosphorus, the arsenic, the fluorine and the chlorine is smaller than 0.1 mg/Nm<3>, and the purifying agent is also used for purifying and concentrating CO from the calcium carbide furnace exhaust. Compared with the prior art, the purifying agent disclosed by the invention has the beneficial effects that metals such as ferrum, zinc, copper, molybdenum, silver and nickel are taken as active components, and the A-X combined zeolite is taken as the vector, so that removal of the sulphur, phosphorus, arsenic, fluorine and chlorine in the calcium carbide furnace exhaust is achieved by using a one-step method; the purifying flow of the calcium carbide furnace exhaust is simplified; the purification cost is reduced; the content of each of all impurities in the purified calcium carbide furnace exhaust is smaller than 0.1 mg/Nm<3>; the requirements of resource utilization of carbon monoxide can be completely met.
Description
Technical field
The present invention relates to cleanser, especially a kind of cleanser of calcium carbide stove exhaust and the method for utilizing this cleanser purifying calcium carbide furnace tail gas in industrial tail gas purification.
Background technology
Calcium carbide is the important base stock of organic synthesis industry, and the carbide acetylene of take can be produced polyvinyl chloride, neoprene, polyvinyl alcohol, acetylene carbon black, trichloro-ethylene etc. as raw material, also makes the desulfurizing agent of iron and steel, also for Metal Cutting and welding gas.Polyvinyl chloride (PVC) industry is the main consumer 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, and within 2010, calcium carbide production capacity is 2,200 ten thousand tons, 1,500 ten thousand tons of output.
It is traditional high pollution, high energy consumption industry that calcium carbide is produced.One ton of about 400Nm of calcium carbide by-product calcium carbide stove exhaust of the every production of closed type calcium carbide furnace
3.In calcium carbide stove exhaust, comprise CO, sulfide, fluoride, the contour polluter of chloride.Only by raw calcium carbide stove exhaust 4,000,000,000 Nm of the closed calcium carbide output 1000 annual common property of Wan Dunji， China
3above, there are the Toxics such as 6000 tons of tar, 1810 tons of fluorides, 6500 tons of sulfide to enter atmosphere.If adopt Cress technology, tar, fluorine, sulphur refuse can harmless processing and utilizing, the CO resource of annual recoverable, amount to 2,090,000 tons of standard coals above, reduce discharging 2,000,000 tons of CO
2.
It is very complicated that calcium carbide stove exhaust forms, must be to its purification in addition before comprehensive utilization.But purification techniques difficulty is very large, there is no at present maturation, advanced feasible industrialization clearer production technology and equipment both at home and abroad, therefore recovery utilization rate is very low, mostly directly emptying or light discharge, small part is 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 less than 5 billion cubic meters, utilization rate less than 10%.Therefore, exploitation is advanced, calcium carbide stove exhaust purification clean technologies are extremely urgent reliably.
At present, the impurity removal in calcium carbide stove exhaust mainly contains wet method and dry technique technique.The hypertoxic waste water that has phosphorous, arsenic, fluorine, chlorine, sulphur etc. after Wet technique washing produces, and environment is caused to very big pollution.Dry technique utilizes chemisorbed principle, adopt active metal to remove impurity, but these current cleansers is very difficult simultaneously clean by above-mentioned several Impurity removals, need to remove step by step, waste time and energy, complex process.
Summary of the invention
The object of this invention is to provide a kind of simple, efficient cleanser that simultaneously removes fluoride, chloride, phosphide, arsenide and sulfide in calcium carbide stove exhaust, be used in calcium carbide stove exhaust purification method, particularly be used in the method for calcium carbide stove exhaust purification concentrate CO, with method for simplifying processing step.
Another object of the present invention is to provide a kind of preparation method of above-mentioned cleanser.
Another object of the present invention is to provide the application of above-mentioned cleanser, and above-mentioned cleanser is purified for calcium carbide stove exhaust, is further used for calcium carbide stove exhaust and purifies in concentrate CO.
A cleanser, take A-X combined zeolite as carrier, supported active metal component.To account for the mass percent of cleanser, load capacity is preferably 1%-45%, more preferably 5%-35%.
Preferably, active metal component is selected from following three groups: iron oxide and/or zinc oxide; Copper and/or molybdenum; Silver and/or nickel.
Preferably, A-X combined zeolite is comprised of the Wessalith CS of 15%-65% weight and the X zeolite of 35%-85% weight.Preferred, A-X combined zeolite is comprised 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 high silicon X-shaped zeolite, 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, and Si/Al atomic ratio is at the high silicon X-shaped zeolite that is called higher than 1.2.
Applicant is through experiment showed, that, in A-X combined zeolite, low-silica X zeolite is better for the effect that removes fluorine in calcium carbide stove exhaust, chlorine, phosphorus, arsenic, sulphur as carrier.
Therefore, Si/Al atomic ratio of X zeolite is preferably 0.90-1.2, more preferably 1-1.1.
A method for the cleanser of above-mentioned purifying calcium carbide furnace tail gas, comprising:
(1) under room temperature, abundant stirring condition, press SiO
2/ Al
2o
3mol ratio 1.2-3.6, preferred 1.8-2.5, sodium silicate aqueous solution is added rapidly in sodium aluminate aqueous solution, form gel, stir 1 hour-2 hours, move in stainless steel crystallizer, standing aging 2 hours-4 hours, at 40 ℃-110 ℃, preferably 55-95 ℃ was carried out alternating temperature crystallization, the temperature of controlling alternating temperature crystallization comprises 70 ℃ of above temperature and 70 ℃ of following temperature, within 30 hours-80 hours, post crystallization completes, and filters, by deionized water washing three times for solid, at 90 ℃-110 ℃, be dried, obtain A-X combined zeolite powder;
(2) by the aqueous solution of the zeolite powder making, the sesbania powder, iron oxide and/or the zinc oxide that account for cleanser mass percent 1%-18%, copper sulphate and/or nitric acid molybdenum, silver nitrate and/or nickel nitrate, extrusion, at 420 ℃-680 ℃, roasting is 5 hours-6 hours, obtains.
Generally, at higher temperature, can promote the generation of A type zeolite under as more than 70 ℃ condition.Therefore, in order to obtain the combined zeolite powder of A-X intersection symbiosis, the alternating temperature crystallization process of step (1) need to be controlled and for part process, at 70 ℃, carry out above part process and carry out below at 70 ℃, by crystallization control temperature, can control A type crystalline element in product and the relative quantity of X-type crystalline element.
Further preferred, in order to obtain more low-silica X zeolite, at least part of crystallization process need to be controlled at 60 ℃ to carry out below.
Preferably, the alternating temperature crystallization range of above-mentioned steps (1) is 55 ℃-95 ℃.
Above-mentioned cleanser removes sulphur, phosphorus, arsenic, fluorine, chlorine for calcium carbide stove exhaust, under 60-280 ℃ of condition, preferably under 100-200 ℃ of condition, by chemisorbed, get rid of sulphur, phosphorus, arsenic, fluorine, the chlorine in calcium carbide stove exhaust, sulphur, phosphorus, arsenic, fluorine, chlorinity can be removed to respectively≤0.1 mg/ Nm
3.
Above-mentioned cleanser purifies concentrate CO for calcium carbide stove exhaust, comprises the following steps successively: the dedusting of raw material calcium carbide furnace gas, cooling decoking, Temp .-changing adsorption preliminary clearning, supercharging, sulfur-resistant catalytic deoxidization, hydrolysis desulfurization, depickling gas, essence desulfurization, phosphorus, arsenic, fluorine, chlorine, smart deoxidation, dry, pressure-changed adsorption concentrating CO.
Existing calcium carbide stove exhaust purifies in the method technique of concentrate CO, conventionally need to pass through ten multiple working procedures such as dedusting, cooling decoking, Temp .-changing adsorption preliminary clearning, supercharging, sulfur-resistant catalytic deoxidization, hydrolysis desulfurization, depickling gas, smart dephosphorization, smart dearsenification, smart defluorinate, smart dechlorination, smart desulfurization, smart deoxidation, dry, pressure-changed adsorption concentrating CO, technological process is complicated, purifies cost high.And the present invention is by a kind of new cleanser, disposable while deep removal sulphur, phosphorus, arsenic, fluorine, chlorine, simplified calcium carbide stove exhaust purification process, for calcium carbide stove exhaust, purify the method technique of concentrate CO, for the processing of calcium carbide furnace gas waste gas, the recycling of CO provides larger convenient.
Research shows, the cleanser of load iron oxide, zinc oxide is better to the removal effect of sulphur, the cleanser of copper, molybdenum isoreactivity metal has good removal effect to phosphorus and arsenide, the metals such as silver, nickel are that active cleanser has good removal effect to fluorine and chloride, 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, and the requirement of carrier is also had nothing in common with each other.All the more so while especially using zeolite as cleanser carrier.Applicant finds through great many of experiments, Wessalith CS carrier is removing better as hydrogen sulfide to the sulfide of the less phosphide of molecular diameter, fluoride and molecular weight, and X zeolite carrier is as better in benzothiophene removal effect to the larger sulfide of the larger arsenide of molecular diameter, chloride and molecular weight, with single Wessalith CS or X zeolite, makes carrier and be difficult to the impurity such as the sulphur in calcium carbide stove exhaust, phosphorus, arsenic, fluorine, chlorine to remove totally simultaneously.The present invention be take A-X combined zeolite as carrier, three kinds or three kinds of above components in a certain amount of zinc of load, iron, copper, molybdenum, silver, nickel isoreactivity metal, adopt kneading method to prepare calcium carbide stove exhaust cleanser, prepare functional, constitutionally stable cleanser, realized effective removal of sulphur, phosphorus, arsenic, fluorine, the contour polluter of chlorine in calcium carbide stove exhaust.
Compared with prior art, it is active component that the metals such as zinc, iron, copper, molybdenum, silver, nickel are take in the present invention, usings A-X combined zeolite as carrier, makes the adsorption layer pore-size distribution of cleanser more extensive, and the impurity of different pore size is had to good assimilation effect.By one-step method, just can realize the removing of sulphur in calcium carbide stove exhaust, phosphorus, arsenic, fluorine, chlorine, simplify calcium carbide stove exhaust purification process, reduce purification cost.After purifying, in calcium carbide stove exhaust, the content of all impurity is all less than 0.1 mg/ Nm
3, can meet the requirement of the recycling of carbon monoxide completely.
The specific embodiment
Disclosed all features 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.
Disclosed arbitrary feature in this description (comprising any accessory claim, summary), unless narration especially all can be replaced by other equivalences or the alternative features with similar object.That is,, unless narration especially, each feature is an example in a series of equivalences or similar characteristics.
Embodiment 1 prepares cleanser I
(1) take 600 grams of sodium metasilicate (SiO
2content 27.1wt%) be dissolved in 2400 ml deionized water, under room temperature, abundant 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 move in 1 liter of stainless steel crystallizer, and standing aging 2-4 hour, warming-in-water to 57 ℃, crystallization is warming-in-water to 98 ℃ after 28 hours, and crystallization completes reaction for 13 hours.Filter, solid with 600 ml deionized water washing three times, is dried at 90 ℃ respectively, obtains the combined zeolite powder of A-X intersection symbiosis.
X-ray diffraction is analyzed (XRD analysis) and is shown, in combined zeolite containing 34% A type zeolite and 66% X-type zeolite, Si/Al mol ratio 1.04:1.
(2) take zeolite powder, 7g sesbania powder, the 23 grams of cupric sulfate pentahydrates in 65 grams of steps (1), 9 grams of zinc oxide, 8 grams of silver nitrates, and 12 milliliters of aqueous solution, extrusion, at 520 ℃, roasting is 5 hours, is purified agent I.
The Contrast on effect embodiment of 2 three kinds of cleansers of embodiment
Utilize the preparation method of embodiment 1, the A-X combined zeolite powder that adopts commercially available A type zeolite to replace step (1) to obtain, prepare cleanser II, the A-X combined zeolite powder that adopts commercially available low-silica X zeolite (Si/Al atomic ratio 1.03) to replace step (1) to obtain, prepares cleanser III.
Three kinds of cleansers are loaded on respectively in fixed adsorption bed, investigate their removal effects to impurity such as phosphide, arsenide, sulfide, fluoride, chlorides.
Table 1 calcium carbide furnace gas component
Operating condition: DN25 reaction tube, void tower linear speed: 0.05m/s, the time of staying: 20s, operating temperature: 110 ℃, operating pressure: 0.5MPa, purification result is as follows:
The clean-up effect of table 2 cleanser I to calcium carbide stove exhaust
The clean-up effect of table 3 cleanser II to calcium carbide stove exhaust
The clean-up effect of table 4 cleanser III to calcium carbide stove exhaust
Result from table 2-4, compare as the cleanser (cleanser III) of carrier with single low-silica X zeolite as the cleanser (cleanser II) of carrier with single A type zeolite, by A-X combined zeolite, as the cleanser of carrier, the phosphorus in calcium carbide stove exhaust, arsenic, fluorine, chlorine, sulfide being had to good removal effect, is a kind of desirable cleanser.
Embodiment 3 cleanser I purify the effect embodiment of concentrate CO for calcium carbide stove exhaust
Table 5 feed gas composition
Table 6 impurity composition
High temperature calcium carbide furnace gas (500-800 ℃) enters decoking device after ceramic filter dedusting, after heat exchange, be cooled to 30 ℃, tar solidifies separates out, be forced into 0.6MPa, enter sulfur-tolerance deoxidation system, utilize the heat supply of high temperature unstripped gas, under sulfur-tolerance deoxidation catalyst effect, at 210 ℃, air speed 2200h
-1under condition, react, then enter the hydrolysis desulfurization process of hydrolysis desulfurizing agent, at 140 ℃, air speed 2200h
-1the desulfurization that is hydrolyzed under condition, makes organic sulfur be converted into hydrogen sulfide, enters afterwards alkali cleaning depickling gas unit, with alkali lye such as NaOH, acid gas is removed, after depickling, gas enters smart desulfurization, phosphorus, arsenic, fluorine, chlorine technical unit, under the effect of cleanser I, and 130 ℃, air speed 2500h
-1under condition, purify, then enter palladium dehydrogenation catalyst system, at 60 ℃, air speed 4500h
-1under condition, carry out smart deoxidation, molecular sieve drying, last Pressure Swing Adsorption, the carbon monoxide product gas obtaining, the component of gas product is in Table 7, and each impurity composition measurement result in gas product is in Table 8.
Table 7 gas product component
Table 8 impurity composition
From the result of table 7 and table 8, in gas product, carbonomonoxide concentration is greater than 98%, and the content of all impurity is all less than 0.1 Mg/Nm
3, can meet the recycling of carbon monoxide gas completely, show this feasible process.
The present invention is not limited to the aforesaid specific embodiment.The present invention expands to any new feature or any new combination disclosing in this manual, and the arbitrary new method disclosing or step or any new combination of process.
Claims (10)
1. a calcium carbide stove exhaust cleanser, is characterized in that, take A-X combined zeolite as carrier, supported active metal component.
2. cleanser as claimed in claim 1, is characterized in that, described active metal component is selected from following three groups: iron oxide and/or zinc oxide; Copper and/or molybdenum; Silver and/or nickel.
3. cleanser as claimed in claim 2, is characterized in that, to account for the mass percent of cleanser, the load capacity of described active metal is 1%-45%, is preferably 5%-35%.
4. cleanser as claimed in claim 1, is characterized in that, described A-X combined zeolite is comprised of the Wessalith CS of 15%-65% weight and the X zeolite of 35%-85% weight, preferably the Wessalith CS of 25%-55% weight and the X zeolite of 45%-75% weight, consists of.
5. cleanser as claimed in claim 4, is characterized in that, Si/Al atomic ratio of described X zeolite is 0.90-1.2, is preferably 1-1.1.
6. a method of preparing the calcium carbide stove exhaust cleanser as described in arbitrary claim in claim 1-5, is characterized in that, comprising:
(1) under room temperature, abundant stirring condition, press SiO
2/ Al
2o
3mol ratio 1.2-3.6, preferred 1.8-2.5, sodium silicate aqueous solution is added rapidly in sodium aluminate aqueous solution, form gel, stir 1 hour-2 hours, move in stainless steel crystallizer, standing aging 2 hours-4 hours, at 40 ℃-110 ℃, preferably 55-95 ℃ was carried out alternating temperature crystallization, the temperature of controlling alternating temperature crystallization comprises 70 ℃ of above temperature and 70 ℃ of following temperature, within 30 hours-80 hours, post crystallization completes, and filters, by deionized water washing three times for solid, at 90 ℃-110 ℃, be dried, obtain A-X combined zeolite powder;
(2) by the aqueous solution of the zeolite powder making, the sesbania powder, iron oxide and/or the zinc oxide that account for cleanser mass percent 1%-18%, copper sulphate and/or nitric acid molybdenum, silver nitrate and/or nickel nitrate, extrusion, at 420 ℃-680 ℃, roasting is 5 hours-6 hours, obtains.
7. preparation method as claimed in claim 6, is characterized in that, described crystallization process part is carried out below at 60 ℃.
8. preparation method as claimed in claim 6, is characterized in that, the alternating temperature crystallization temperature of described step (1) is 55-95 ℃.
9. the method for the utilization cleanser purifying calcium carbide furnace tail gas as described in arbitrary claim in claim 1-5, it is characterized in that, utilize cleanser at 60-280 ℃, preferably under 100-200 ℃ of condition, remove sulphur, phosphorus, arsenic, fluorine, the chlorine of calcium carbide stove exhaust, make its content all be less than 0.1 mg/ Nm
3.
10. the cleanser of utilization as described in arbitrary claim in claim 1-5 purifies a method of concentrate CO from calcium carbide stove exhaust, it is characterized in that, comprises the following steps successively: the dedusting of raw material calcium carbide furnace gas, cooling decoking, Temp .-changing adsorption preliminary clearning, supercharging, sulfur-resistant catalytic deoxidization, hydrolysis desulfurization, depickling gas, smart desulfurization, phosphorus, arsenic, fluorine, chlorine, smart deoxidation, dry, pressure-changed adsorption concentrating CO.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694989A (en) * | 2016-02-03 | 2016-06-22 | 山东佳星环保科技有限公司 | High-temperature coal gas purification technique |
| CN106517203A (en) * | 2016-11-09 | 2017-03-22 | 重庆鸿庆达产业有限公司 | Calcium carbide production system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341474A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp.-change adsorptive process |
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
-
2013
- 2013-10-31 CN CN201310527354.7A patent/CN103551105A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341474A (en) * | 2000-08-28 | 2002-03-27 | 波克股份有限公司 | Temp.-change adsorptive process |
| CN102627280A (en) * | 2011-07-14 | 2012-08-08 | 西南化工研究设计院 | Method for purifying and concentrating CO from calcium carbide furnace gas |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105694989A (en) * | 2016-02-03 | 2016-06-22 | 山东佳星环保科技有限公司 | High-temperature coal gas purification technique |
| CN106517203A (en) * | 2016-11-09 | 2017-03-22 | 重庆鸿庆达产业有限公司 | Calcium carbide production system |
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Application publication date: 20140205 |