CN103506072B - Purifying agent for adsorption of sulfides in olefin tail gas and preparation method thereof - Google Patents
Purifying agent for adsorption of sulfides in olefin tail gas and preparation method thereof Download PDFInfo
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- CN103506072B CN103506072B CN201210209800.5A CN201210209800A CN103506072B CN 103506072 B CN103506072 B CN 103506072B CN 201210209800 A CN201210209800 A CN 201210209800A CN 103506072 B CN103506072 B CN 103506072B
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Abstract
The invention belongs to the field of air pollution purification, discloses a purifying agent for chemical adsorption and purification of sulfides in olefin tail gas at the normal temperature and a preparation method thereof. The preparation method comprises the steps: impregnating activated carbon in an aqueous solution containing a soluble iron salt, a soluble sodium salt and a soluble potassium salt, stirring to load the iron salt, the sodium salt and the potassium salt on the activated carbon carrier, then drying, carrying out oxidation treatment, washing, and drying again to obtain the finished product purifying agent. The purifying agent provided by the invention is simple in composition, easy to obtain, low in cost, simple in preparation process and low in production cost, and has easily available raw materials and no environmental pollution. The purifying agent filled into a purifying pipe can be widely applicable to purification of ppm-level sulfides contained in olefin tail gas used in factories and laboratories, enables the content of the purified sulfides to be less than 30 ppb (volume fraction), has the advantages of high sulfide adsorption selectivity, high sulfide adsorption capacity and convenient application, and has important popularization value.
Description
Technical field
The present invention relates to a kind of cleanser removing sulfide, be specifically related to a kind of cleanser by sulfide harmful in alkene tail gas in chemisorbed removing industrial production or experimentation, the invention belongs to field of air pollution purification.
Background technology
China's import place of production is that in the crude oil in the Middle East, sulfur compound is higher.It is also general higher that China coastal seas produces crude oil medium sulphide content content.Along with the continuous intensification of oil extraction, in oil product impurity content particularly sulfide in the trend that rises year by year.The on the other hand domestic change of oil plant crude oil, the improving constantly of the improvement of deep process technology and working ability, cause sulfide to be present in widely in different refined oil product.The product of high-sulfur oil product secondary operations gained, as in the polymerization process such as propylene, ethene, deep-processing process and laboratory analysis process, the sulfide of alkene tail gas produces threat safely to surrounding people.
Gaseous sulfide normally has the material of severe toxicity to human body.For hydrogen sulfide, for there being the colourless gas of rotten egg smell under usual state, just pungent stink can be smelt 10ppb concentration people.Reaching 100ppm in concentration just can cause people poisoning, when concentration reaches 1000ppm, and just can causing death immediately.When Human body package is in the hydrogen sulfide gas of 600ppm concentration 30 minutes fatal.When being exposed in the hydrogen sulfide gas of 800ppm concentration 5 minutes fatal.Therefore national environmental standard, the hydrogen sulfide gas maximum permissible concentration in environment is 10 × 10
-6mg/m
3.
At present, the sulfur method that state's internal olefin tail gas adopts mainly contains damp process and dry process, damp process is exchanged by gas-liquid to be transferred in liquid phase by the sulfide in gas, there is higher sulfur capacity, dry process by gas-solid exchange by the sulfur compounds adsorption in gas in desulfurizing agent, have higher desulfurization precision.Alkene desulfurization patent document very mistake, all concentrates in alkene preparation and production process and causes catalyst poisoning inactivation and to the mordant sulfide aspect of production equipment.As Chinese patent CN101450302A discloses a kind of C 4 olefin desulfurization absorbent and method for making and application.Desulfurizing agent is applied in depollution of environment field owing to requiring that desulfurization precision is very high, domestic also do not have patent report.
Summary of the invention
The invention discloses a kind of for normal temperature by cleanser of chemisorbed purification of light olefins tail gas medium sulphide content and preparation method thereof, aim to provide a kind of its and there is the cleanser of the adsorption cleaning alkene tail gas medium sulphide content that composition is simple, cheap, use cost is low.
The present invention adopts following technical scheme to realize:
The cleanser absorbing alkene tail gas medium sulphide content is carrier by active carbon, and the molysite of solubility, soluble sodium salt, soluble potassium salt are active component., soluble ferric iron salt is 0.5 ~ 3.0% in cleanser by percentage to the quality, and soluble sodium salt is 0.2 ~ 1.5%, and soluble potassium salt is 0.5 ~ 2.5%, carrier
active carbonbe 93.0 ~ 98.0%, finally with nitric acid and hydrogen peroxide, oxidation processes carried out to active component.
Preferred content scope: soluble ferric iron salt is 1.0 ~ 2.0% by percentage to the quality, soluble sodium salt is 0.5 ~ 1.0%, soluble potassium salt is 0.5 ~ 1.5%, and carrier active carbon is 95.5 ~ 98%.
Described active carbon index is bulk density 0.45g/ml, hardness 97, particle size 0.6 ~ 1.7mm, ash content 2%(wt).
The molysite of described solubility is iron chloride, soluble sodium salt is NaOH or sodium carbonate, solubility sylvite be potassium chloride, potassium hydroxide, potash.Above-mentioned any one can be carried on the molysite of the solubility on carrier, soluble sodium salt, solubility sylvite all can be used for this invention.
Cleanser preparation method of the present invention comprises following processing step:
(1) soluble ferric iron salt, soluble sodium salt, soluble potassium salt are mixed with the aqueous solution; In its aqueous solution, by percentage to the quality, be 2.5 ~ 5.0% containing soluble ferric iron salt, soluble sodium salt be 0.25 ~ 2.8%, soluble potassium salt 0.60 ~ 2.0%, surplus is water.
(2) absorbent charcoal carrier is immersed in the aqueous solution containing soluble ferric iron salt, soluble sodium salt, soluble potassium salt, at ambient temperature, stir 4 ~ 6 hours, make molysite, sodium salt, sylvite be carried on absorbent charcoal carrier, obtain the solution of supported active metals carrier;
(3), by the solution of described supported active metals carrier, under baking temperature 70 ~ 80 DEG C of conditions, dry 6 ~ 8 hours, the particle of supported active metals carrier is obtained.
(4) by the particle of described supported active metals carrier, after nitric acid with 68% ~ 70% and the hydrogen peroxide mixed solution of 50% carry out oxidation processes, with distilled water washing (pH value 5), under baking temperature 115 ~ 120 DEG C of conditions, dry 8 ~ 10 hours, obtain finished product cleanser.By percentage to the quality, soluble ferric iron salt is 1.0 ~ 2.0%, soluble sodium salt is 0.5 ~ 1.0%, soluble potassium salt is 0.5 ~ 1.5%.Carrier active carbon is 95.5 ~ 98%.
The invention has the beneficial effects as follows: the normal temperature cleanser for adsorbs olefins tail gas medium sulphide content provided by the invention, its composition is simple, easily obtains, with low cost, and cleanser preparation process is simple, and raw material is easy to get, and production cost is low, non-environmental-pollution.Cleanser loads in purification pipe the purification that can be widely used in containing ppm level sulfide in factory and use for laboratory alkene tail gas, purification after cure thing content is less than 30ppb (volume fraction), have to the adsorptive selectivity of sulfide and adsorption capacity high, apply advantage easily.
Accompanying drawing explanation
Fig. 1 is that finished product cleanser loads purification pipe schematic diagram;
Fig. 2 is containing 5.2ppm (volume fraction) hydrogen sulfide gas, 5.4ppm (volume fraction) cos gas, 5.5ppm(volume fraction) methyl mercaptan gas, 5.1ppm (volume fraction) methyl sulfide gas, 3.7ppm (volume fraction) carbon disulfide gas, the ethene of 3.5ppm (volume fraction) thiophene gas, propylene, butylene gaseous mixture gas-chromatography monitoring system comparison diagram before and after cleanser absorbs.
Detailed description of the invention
Below, by reference to the accompanying drawings and specific embodiment, several embodiments of invention are further described.
Embodiment 1
Take 3.0g iron chloride containing ten crystallizations water, 0.5g NaOH, 0.9g potassium hydroxide and 100mL water were mixed with mixed solution, are then immersed by 40g activated carbon granule in the mixed solution prepared, in stirred at ambient temperature 4 hours.Dry 6 hours at 80 DEG C, obtain the particle of supported active metals carrier.By the particle of supported active metals carrier immerse 68%-70% nitric acid and 50% hydrogen peroxide mixed solution in, until no longer include gas produce.Detecting its pH value with distilled water washing after filtering out particle is 5.Under baking temperature 115 DEG C of conditions, dry 10 hours, obtain finished product cleanser.Cleanser active component: iron chloride mass percent is 1.1%, NaOH mass percent is 1.0%, and potassium hydroxide mass percent is 1.5%; Carrier quality percentage is 96.4%.
As accompanying drawing 1, cleanser 2 being loaded internal diameter is 15mm, and in the pipe of long 100mm, pipe two ends 1,3 are threaded for airtight.Containing 5.2ppm (volume fraction) hydrogen sulfide gas, 5.4ppm (volume fraction) cos gas, 5.5ppm(volume fraction) methyl mercaptan gas, 5.1ppm (volume fraction) methyl sulfide gas, 3.7ppm (volume fraction) carbon disulfide gas, the ethene of 3.5ppm (volume fraction) thiophene gas, propylene, butylene gaseous mixture pass into the purification pipe that cleanser is housed with 100mL/min.Continuing purge is gas-chromatography monitoring spectrogram 2 after 10 hours, illustrates that being cleaned absorption is less than 30ppb (volume fraction).
Embodiment 2
Take 4.3g iron chloride containing ten crystallizations water, 0.3g NaOH, 1.0g potassium chloride and 100mL water were mixed with mixed solution, are then immersed by 40g activated carbon granule in the mixed solution prepared, in stirred at ambient temperature 6 hours.Dry 8 hours at 70 DEG C, obtain the particle of supported active metals carrier.By the particle of supported active metals carrier immerse 68%-70% nitric acid and 50% hydrogen peroxide mixed solution in, until no longer include gas produce.Detecting its pH value with distilled water washing after filtering out particle is 5.Under baking temperature 120 DEG C of conditions, dry 8 hours, obtain finished product cleanser.Cleanser active component: iron chloride mass percent is 1.6%, NaOH mass percent is 0.5%, and potassium chloride mass percent is 0.8%; Carrier quality percentage is 97.1%.
As accompanying drawing 1, cleanser 2 being loaded internal diameter is 15mm, and in the pipe of long 100mm, pipe two ends 1,3 are threaded for airtight.Containing 5.2ppm (volume fraction) hydrogen sulfide gas, 5.4ppm (volume fraction) cos gas, 5.5ppm(volume fraction) methyl mercaptan gas, 5.1ppm (volume fraction) methyl sulfide gas, 3.7ppm (volume fraction) carbon disulfide gas, the ethene of 3.5ppm (volume fraction) thiophene gas, propylene, butylene gaseous mixture pass into the purification pipe that cleanser is housed with 100mL/min.Continuing purge is gas-chromatography monitoring spectrogram 2 after 10 hours, illustrates that being cleaned absorption is less than 30ppb (volume fraction).
Embodiment 3
Take 2.7g iron chloride containing ten crystallizations water, 1.5g sodium carbonate containing ten crystallizations water, 0.7g potash and 100mL water were mixed with mixed solution, are then immersed by 40g activated carbon granule in the mixed solution prepared, in stirred at ambient temperature 4 hours.Dry 6 hours at 80 DEG C, obtain the particle of supported active metals carrier.By the particle of supported active metals carrier immerse 68%-70% nitric acid and 50% hydrogen peroxide mixed solution in, until no longer include gas produce.Detecting its pH value with distilled water washing after filtering out particle is 5.Under baking temperature 115 DEG C of conditions, dry 8 hours, obtain finished product cleanser.Cleanser active component: iron chloride mass percent is 1.0%, carbonating sodium mass percent is 0.5%, and potash mass percent is 0.5%; Carrier quality percentage is 98.0%.
As accompanying drawing 1, cleanser 2 being loaded internal diameter is 15mm, and in the pipe of long 100mm, pipe two ends 1,3 are threaded for airtight.Containing 5.2ppm (volume fraction) hydrogen sulfide gas, 5.4ppm (volume fraction) cos gas, 5.5ppm(volume fraction) methyl mercaptan gas, 5.1ppm (volume fraction) methyl sulfide gas, 3.7ppm (volume fraction) carbon disulfide gas, the ethene of 3.5ppm (volume fraction) thiophene gas, propylene, butylene gaseous mixture pass into the purification pipe that cleanser is housed with 100mL/min.Continuing purge is gas-chromatography monitoring spectrogram 2 after 10 hours, illustrates that being cleaned absorption is less than 30ppb (volume fraction).
Embodiment 4
Take 5.4g iron chloride containing ten crystallizations water, 2.9g sodium carbonate containing ten crystallizations water, 2.0g potassium chloride and 100mL water were mixed with mixed solution, are then immersed by 40g activated carbon granule in the mixed solution prepared, in stirred at ambient temperature 6 hours.Dry 8 hours at 70 DEG C, obtain the particle of supported active metals carrier.By the particle of supported active metals carrier immerse 68%-70% nitric acid and 50% hydrogen peroxide mixed solution in, until no longer include gas produce.Detecting its pH value with distilled water washing after filtering out particle is 5.Under baking temperature 115 DEG C of conditions, dry 8 hours, obtain finished product cleanser.Active component: iron chloride mass percent is 2.0%, carbonating sodium mass percent is 1.0%, and potassium chloride mass percent is 1.5%; Carrier quality percentage is 95.5%.
As accompanying drawing 1, cleanser 2 being loaded internal diameter is 15mm, and in the pipe of long 100mm, pipe two ends 1,3 are threaded for airtight.Containing 5.2ppm (volume fraction) hydrogen sulfide gas, 5.4ppm (volume fraction) cos gas, 5.5ppm(volume fraction) methyl mercaptan gas, 5.1ppm (volume fraction) methyl sulfide gas, 3.7ppm (volume fraction) carbon disulfide gas, the ethene of 3.5ppm (volume fraction) thiophene gas, propylene, butylene gaseous mixture pass into the purification pipe that cleanser is housed with 100mL/min.Continuing purge is gas-chromatography monitoring spectrogram 2 after 10 hours, illustrates that being cleaned absorption is less than 30ppb (volume fraction).
The foregoing is only better possible embodiments of the present invention, not thereby limit to the scope of the claims of the present invention, therefore the equivalent structure change that every utilization description of the present invention and accompanying drawing content are done, be all contained in protection scope of the present invention.
Claims (5)
1. the cleanser for adsorbs olefins tail gas medium sulphide content, be carrier by active carbon, the molysite of solubility, soluble sodium salt, soluble potassium salt are active component, in cleanser by percentage to the quality, soluble ferric iron salt is 0.5 ~ 3.0%, soluble sodium salt is 0.2 ~ 1.5%, and soluble potassium salt is 0.5 ~ 2.5%, and active carbon is 93.0 ~ 98.0%.
2. the cleanser for adsorbs olefins tail gas medium sulphide content according to claim 1, it is characterized in that, by percentage to the quality, soluble ferric iron salt is 1.0 ~ 2.0%, soluble sodium salt is 0.5 ~ 1.0%, soluble potassium salt is 0.5 ~ 1.5%, and active carbon is 95.5 ~ 98%.
3. the cleanser for adsorbs olefins tail gas medium sulphide content according to claim 1, is characterized in that, described active carbon index is bulk density 0.45g/ml, hardness 97, particle size 0.6 ~ 1.7mm, ash content 2% (wt).
4. the cleanser for adsorbs olefins tail gas medium sulphide content according to claim 1, it is characterized in that, the molysite of described solubility is iron chloride, and described soluble sodium salt is NaOH or sodium carbonate, and the sylvite of described solubility is potassium chloride, potassium hydroxide, potash.
5., for a preparation method for adsorbs olefins tail gas medium sulphide content cleanser, comprise following processing step:
(1) soluble ferric iron salt, soluble sodium salt, soluble potassium salt are mixed with the aqueous solution; In its aqueous solution, by percentage to the quality, be 2.5 ~ 5.0% containing soluble ferric iron salt, soluble sodium salt be 0.25 ~ 2.8%, soluble potassium salt 0.60 ~ 2.0%, surplus is water;
(2) active carbon is immersed in the aqueous solution containing soluble ferric iron salt, soluble sodium salt, soluble potassium salt, at ambient temperature, stir 4 ~ 6 hours, make molysite, sodium salt, sylvite be carried on absorbent charcoal carrier, obtain the solution of supported active metals carrier;
(3), by the solution of described supported active metals carrier, under baking temperature 70 ~ 80 DEG C of conditions, dry 6 ~ 8 hours, the particle of supported active metals carrier is obtained;
(4), by the particle of described supported active metals carrier, after carrying out oxidation processes with 68% ~ 70% nitric acid and 50% hydrogen peroxide mixed solution, with distilled water washing, under baking temperature 115 ~ 120 DEG C of conditions, dry 8 ~ 10 hours, agent is purified.
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|---|---|---|---|
| CN201210209800.5A CN103506072B (en) | 2012-06-19 | 2012-06-19 | Purifying agent for adsorption of sulfides in olefin tail gas and preparation method thereof |
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| CN201210209800.5A CN103506072B (en) | 2012-06-19 | 2012-06-19 | Purifying agent for adsorption of sulfides in olefin tail gas and preparation method thereof |
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| CN103506072B true CN103506072B (en) | 2015-05-13 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4556547A (en) * | 1982-02-01 | 1985-12-03 | Takeda Chemical Industries, Ltd. | Process for treatment of gases |
| CN1253847A (en) * | 1998-11-13 | 2000-05-24 | 中国石油化工集团公司 | Desulfurizer for refining gas and its preparation method |
| US6217839B1 (en) * | 1999-08-20 | 2001-04-17 | Uop Llc | Removal of sulfur compounds from gaseous waste streams |
| CN101590395A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of load-type desulfurizer |
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| CN102099115B (en) * | 2008-07-14 | 2015-01-21 | 日挥通用株式会社 | Deodorizing catalyst, deodorizing method using same and method for regenerating the catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4556547A (en) * | 1982-02-01 | 1985-12-03 | Takeda Chemical Industries, Ltd. | Process for treatment of gases |
| CN1253847A (en) * | 1998-11-13 | 2000-05-24 | 中国石油化工集团公司 | Desulfurizer for refining gas and its preparation method |
| US6217839B1 (en) * | 1999-08-20 | 2001-04-17 | Uop Llc | Removal of sulfur compounds from gaseous waste streams |
| CN101590395A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of load-type desulfurizer |
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