CN106378196A - Fe-based mercury remover and preparation method thereof - Google Patents
Fe-based mercury remover and preparation method thereof Download PDFInfo
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- CN106378196A CN106378196A CN201610776789.9A CN201610776789A CN106378196A CN 106378196 A CN106378196 A CN 106378196A CN 201610776789 A CN201610776789 A CN 201610776789A CN 106378196 A CN106378196 A CN 106378196A
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- iron
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- mercury removal
- mercury
- active component
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
Abstract
The invention belongs to the technical field of a mercury remover, and more specifically relates to a Fe-based mercury remover and a preparation method thereof. The mercury remover comprises an active component, a carrier and an auxiliary agent, the active component is ferric sulfide, the mass parts of the active component is 19-65%, the mass parts of the carrier is 30-80%, and the mass parts of the auxiliary agent is 1-5%. The ferric sulfide prepared by a deposition technology has high mercury removing capability, the mercury volume can reach 40% or more, the addition of the carrier can guarantee high intensity of the products in a usage process; a band extrusion technology is employed for direct moulding and de-watering to obtain the product mercury remover, gas phase sulfuration is not required, the preparation process is safe; iron is taken as an active metal component for removing mercury, the raw materials are easily acquired, the production cost is low, and the Fe-based mercury remover can promote the development of the metal sulfide mercury remover.
Description
Technical field
The invention belongs to mercury removal agent technical field is and in particular to a kind of iron-based mercury removal agent and preparation method thereof.
Background technology
Hydrargyrum has high volatile, high toxicity and corrosivity, and is widely present in coal-fired flue-gas, natural gas, natural gas condensation
In oil, Petroleum and distillate, in industrial processes, hydrargyrum has serious hazardness, and aluminum heat exchanger can be led to corrode
Bore a hole, so that downstream catalyst is poisoned, reduce catalyst life.In addition, hydrargyrum has serious bio-toxicity, hydrargyrum is inhaled in vivo
The methyl mercury of severe toxicity after receipts, can be formed, combine with the sulfydryl of enzyme, thus the activity of destructive enzyme, enter the methyl of brain
Hydrargyrum can make brain atrophy, encroach on neurocyte, and hydrargyrum has cumulative bad in vivo, and hydrargyrum can lead to after other biological internal enrichments
Cross food chain and be recycled into human body.Therefore, with the continuous development of Chinese society economy, people to environmental problem pay attention to day by day,
The improvement of hydrargyrum becomes current problem demanding prompt solution.
Domestic conventional mercury removal agent species active charcoal mercury removal agent and metal sulfide mercury removal agent.With respect to activated carbon class
Mercury removal agent, metal-oxide mercury removal agent has advantages below：Can be not only used for dry gas and can also be used under moist conditions, pressure is in normal pressure
All can normally use under the conditions of ~ 12Mpa, and sulfur will not can pass through metal because of distillation or solution loss, discarded mercury removal agent
Smelting furnace is recycled.Therefore, metal sulphide type mercury removal agent has broad application prospects.
At present, metal sulphide type mercury removal agent of the prior art is mainly with copper sulfide as main active component, but, make
With copper as demercuration active metal component, relatively costly, thus leading to relevant enterprise heavy load, and in preparation process often
Vulcanization is gas-phase presulfiding, needs to be vulcanized using sulfurous gas such as hydrogen sulfide etc., production process is more dangerous, tail
Gas is difficult to process, and active component is difficult to sulfuration completely, and these shortcomings govern the development of metal sulfide mercury removal agent.
Content of the invention
In order to solve the above-mentioned problems in the prior art, the invention provides a kind of iron-based mercury removal agent and its preparation side
Method.
The technical problem to be solved in the present invention is achieved through the following technical solutions：
A kind of iron-based mercury removal agent, including active component, carrier and auxiliary agent, described active component is iron sulfide, described active component
Mass fraction be 19% ~ 65%, the mass fraction of described carrier is 30% ~ 80%, the mass fraction of described auxiliary agent is 1% ~
5%.
Further illustrating as the present invention, described carrier includes boehmite, α-aluminium hydroxide, fast shedding, hydrogen-oxygen
Change aluminum dry glue powder, molecular sieve, activated carbon, at least one in silicon oxide, described auxiliary agent include CMC, sesbania powder, magnesium stearate,
At least one in maltodextrin.
Further illustrating as the present invention, the silicon oxide in described carrier is added with Ludox form.
The preparation method of above-mentioned mercury removal agent, comprises the steps：
Step one, precipitant is soluble in water, controlling reaction temperature is precipitated agent solution；
Step 2, iron salt solutions are added in described precipitant solution, filter after fully reacting, washing obtains described activearm
Point；
Step 3, described active component and support powder and auxiliary agent are carried out extrusion after mixed grind, obtain product, described product is existed
It is dried in vacuum drying oven, obtain mercury removal agent.
Further illustrating as the present invention, precipitate described in step one include sodium sulfide, ammonium sulfide, in Potassium monosulfide.
At least, described precipitate is dissolved in S in resulting solution after water2-Ion concentration is 3.5 ~ 50 g/L.
Further illustrating as the present invention, precipitant solution reaction temperature described in step one controls -12oC ~
30oC.
Further illustrating as the present invention, iron salt solutions described in step 2 include ferric nitrate, iron sulfate, in iron chloride
At least one.
Further illustrating as the present invention, reaction temperature described in step 2 is -10oC ~ 35oC.
Further illustrating as the present invention, vacuum drying oven baking temperature described in step 3 is 50oBelow C, is dried
Time is 3 ~ 60 h.
Further illustrating as the present invention, product described in step 3 can remove moisture using freeze drying process and obtain
To mercury removal agent.
Compared with prior art, beneficial effects of the present invention：
1st, the iron sulfide prepared by depositing technology, has very high demercuration ability, and its hydrargyrum holds up to more than 40%, but merely
During using iron sulfide, with the carrying out of demercuration reaction, product is understood efflorescence and leads to bed layer pressure to raise it is therefore desirable to add carrier
Higher intensity is had in use with guarantee product；Subsequently obtain into pint using after extrusion technique straight forming, eliminating water
Mercurial.
2nd, it is not required to gas-phase presulfiding, safe preparation process in the preparation method of the present invention；And using ferrum as the activity gold of demercuration
Belong to component, raw material is easy to get, and product cost is low, can promote the development of metal sulfide mercury removal agent.
Specific embodiment
With reference to specific embodiment, further detailed description is done to the present invention, but embodiments of the present invention are not limited to
This.
Embodiment 1：
Weigh 100 g nine water sodium sulfide to be dissolved in 3800 mL water, solution is cooled to -12oC；Separately take 112 g nine water ferric nitrate
It is dissolved in 500 mL water, then iron nitrate solution is added in sodium sulfide solution, controlling reaction temperature is -10oC, reaction completes
Afterwards products therefrom filtered, wash, be subsequently adding boehmite 122 g, CMC 1.5 extrusion after g mixed grind, in vacuum drying
In 20 in caseo60 hs are dried under the conditions of C, obtain finished product mercury removal agent, active component sulfuration iron content 19% in product, carrier intends thin water
Aluminum stone content 80%, auxiliary agent CMC content 1%.
Embodiment 2：
Weigh 113.5 g nine water sodium sulfide to be dissolved in 500 mL water, solution is cooled to 10oC；Separately take 75.6g iron sulfate slow
Add in sodium sulfide solution, controlling reaction temperature is 15oProducts therefrom is filtered after the completion of reaction, washs by C, be subsequently adding α-
Extrusion after aluminium hydroxide 51.5 g, sesbania powder 2.5 g mixed grind, in 20 in vacuum drying oveno60 hs are dried under the conditions of C, must become
Pint mercurial, active component sulfuration iron content 35%, carrier α-aluminium hydroxide content 62%, auxiliary agent sesbania powder content 3% in product.
Embodiment 3：
Weigh ammonium sulfide solution 200 g, solution is cooled to 20oC；Ferric chloride (FeCl36H2O) 95.5g is separately taken to be dissolved in 1000 mL water
In, then ferrum sulfuricum oxydatum solutum is added in ammonium sulfide solution, controlling reaction temperature is 25oC, by products therefrom mistake after the completion of reaction
Filter, washing, are subsequently adding molecular sieve powder 33 g, extrusion after maltodextrin 3.7 g mixed grind, in 30 in vacuum drying ovenoC bar
40 hs are dried under part, obtain finished product mercury removal agent, active component sulfuration iron content 50% in product, carrier molecule sieves content 45%, auxiliary agent
Maltodextrin content 5%.
Embodiment 4：
Weigh ammonium sulfide solution 200 g, solution is cooled to 20oC；Anhydrous ferric trichloride 57.5 g is separately taken to add ammonium sulfide molten
In liquid, controlling reaction temperature is 25oProducts therefrom is filtered after the completion of reaction, washs by C, is subsequently adding fast shedding 20g, hydrogen-oxygen
Extrusion after change aluminum dry glue powder 13 g, maltodextrin 3.7 g mixed grind, in 30 in vacuum drying oveno40 hs are dried under the conditions of C, obtain
Finished product mercury removal agent, active component sulfuration iron content 50%, the fast shedding of carrier and aluminum hydroxide solid elastomer powder total amount 45%, auxiliary agent in product
Maltodextrin content 5%.
Embodiment 5：
Weigh the anhydrous Potassium monosulfide. of 50 g to be dissolved in 1000 mL water, solution temperature is controlled to 30oC；Weigh the acid of 122 g nine liquid glauber salt
Ferrum adds in potassium sulfide solution, and controlling reaction temperature is 35oProducts therefrom is filtered after the completion of reaction, washs, is subsequently adding by C
Extrusion after activated carbon powder 45.7 g, magnesium stearate 1.6 g mixed grind, in 50 in vacuum drying oveno3 hs are dried under the conditions of C, must become
Pint mercurial, active component sulfuration iron content 40%, Carriers Active carbon content 58%, auxiliary agent magnesium stearate content 2% in product.
Embodiment 6：
Weigh the anhydrous Potassium monosulfide. of 50 g to be dissolved in 290 mL water, solution temperature is controlled to 30oC；Weigh the acid of 122 g nine liquid glauber salt
Ferrum is dissolved in 500 mL water, then adds in potassium sulfide solution by iron nitrate solution, and controlling reaction temperature is 35oC, reaction completes
Afterwards products therefrom filtered, wash, be subsequently adding α-aluminium hydroxide 11.5g, 30% Ludox 15 g, magnesium stearate 0.97 g mix
Extrusion after stone roller, in 50 in vacuum drying oveno3 hs are dried under the conditions of C, obtain finished product mercury removal agent, active component iron sulfide in product
Content 65%, carrier α-aluminium hydroxide and silicon oxide total content 33%, auxiliary agent magnesium stearate content 2%.
Embodiment 7：
Weigh 100 g nine water sodium sulfide to be dissolved in 2000 mL water, solution is cooled to -12oC；Separately take 112g nine water ferric nitrate
It is dissolved in 500 mL water, then iron nitrate solution is added in sodium sulfide solution, controlling reaction temperature is -10oC, reaction completes
Afterwards products therefrom filtered, wash, be subsequently adding boehmite 49.5 g, CMC 2.05 g, magnesium stearate 2.05 g mixed grind
Extrusion afterwards, then adopts freeze drying process eliminating water, obtains finished product mercury removal agent, active component sulfuration iron content 35%, carrier in product
Boehmite content 60%, auxiliary agent CMC and magnesium stearate total content 5%.
Embodiment 8：
Control sample is certain commercially available sulfuration cuprio mercury removal agent sample, and it indicates that CuS content is 30%, loading amount：0.1 ml；Granularity：0.25
~ 0.45 mm；Pressure：Normal pressure；Reaction temperature：50oC；Indoor temperature：30oC ；Air speed：1.5 ×105h-1；Unstripped gas group
Become：1:2 methane gas and nitrogen；Mercury content：20 ~ 25 mg/m3.
Inlet gas are adopted with tail gas content《The mensure Cold Atomic Fluorescent Mercury of GB/T 16781.2-1997 Hg in natural gas content
Spectrophotography》It is measured, measure more than 2 mg/m for continuous three times when outlet mercury concentration3When think and penetrate.Mercury removal agent takes out
Afterwards, adopt《The mensure cold atomic absorbent spectrophotometry of GB/T 17136-1997 soil quality total mercury》It is measured.
In above-described embodiment, the test result of prepared mercury removal agent and control sample correlated performance is as shown in table 1,
| Sample number | Hydrargyrum holds (%) |
| Embodiment 1 | 7.0 |
| Embodiment 2 | 11.2 |
| Embodiment 3 | 15.1 |
| Embodiment 4 | 14.7 |
| Embodiment 5 | 11.6 |
| Embodiment 6 | 15.6 |
| Embodiment 7 | 11.5 |
| Embodiment 8（Control sample） | 10.1 |
Table 1
Can draw from mercury removal agent determination of activity result, the iron-based mercury removal agent hydrargyrum appearance of present invention preparation is not less than cuprio mercury removal agent,
It is applied to during gas phase demercuration, there is good demercuration effect, and using ferrum as the active metal component of demercuration, raw material is easy to get, product
Low cost, can promote the development of metal sulfide mercury removal agent.
Above content is to further describe it is impossible to assert with reference to specific preferred implementation is made for the present invention
Being embodied as of the present invention is confined to these explanations.For general technical staff of the technical field of the invention,
On the premise of present inventive concept, some simple deduction or replace can also be made, all should be considered as belonging to the present invention's
Protection domain.
Claims (10)
1. a kind of iron-based mercury removal agent it is characterised in that：Including active component, carrier and auxiliary agent, described active component is iron sulfide,
The mass fraction of described active component is 19% ~ 65%, and the mass fraction of described carrier is 30% ~ 80%, the matter of described auxiliary agent
Amount fraction is 1% ~ 5%.
2. a kind of iron-based mercury removal agent according to claim 1 it is characterised in that：Described carrier include boehmite, α-
Aluminium hydroxide, fast shedding, aluminum hydroxide solid elastomer powder, molecular sieve, activated carbon, at least one in silicon oxide, described auxiliary agent includes
At least one in CMC, sesbania powder, magnesium stearate, maltodextrin.
3. a kind of iron-based mercury removal agent according to claim 2 it is characterised in that：Silicon oxide in described carrier is with Ludox
Form adds.
4. mercury removal agent described in a kind of any one of claims 1 to 3 preparation method it is characterised in that：Comprise the steps：
Step one, precipitant is soluble in water, controlling reaction temperature is precipitated agent solution；
Step 2, iron salt solutions are added in described precipitant solution, filter after fully reacting, washing obtains described activearm
Point；
Step 3, described active component and support powder and auxiliary agent are carried out extrusion after mixed grind, obtain product, described product is existed
It is dried in vacuum drying oven, obtain mercury removal agent.
5. preparation method according to claim 4 it is characterised in that：Precipitate described in step one includes sodium sulfide, sulfur
Change ammonium, at least one in Potassium monosulfide., described precipitate is dissolved in S in resulting solution after water2-Ion concentration is 3.5 ~ 50 g/L.
6. preparation method according to claim 4 it is characterised in that：The control of precipitant solution reaction temperature described in step one
Make -12oC ~ 30oC.
7. preparation method according to claim 4 it is characterised in that：Iron salt solutions described in step 2 include ferric nitrate,
At least one in iron sulfate, iron chloride.
8. preparation method according to claim 4 it is characterised in that：Reaction temperature described in step 2 is -10oC ~
35oC.
9. preparation method according to claim 4 it is characterised in that：Vacuum drying oven baking temperature described in step 3 is
50oBelow C, drying time is 3 ~ 60 h.
10. preparation method according to claim 4 it is characterised in that：Product described in step 3 can be dry using freezing
Drying process removes moisture and obtains mercury removal agent.
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| CN201610776789.9A CN106378196A (en) | 2016-08-31 | 2016-08-31 | Fe-based mercury remover and preparation method thereof |
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| CN201610776789.9A CN106378196A (en) | 2016-08-31 | 2016-08-31 | Fe-based mercury remover and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110756157A (en) * | 2019-11-08 | 2020-02-07 | 浙江大学 | Preparation and demercuration method of supported iron-based mercury adsorbent |
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| US4256707A (en) * | 1979-10-24 | 1981-03-17 | The United States Of America As Represented By The Secretary Of The Interior | Selective removal of mercury from cyanide solutions |
| JPS5637033A (en) * | 1979-08-30 | 1981-04-10 | Dowa Mining Co Ltd | Substance for absorbing mercury in acidic exhaust gas |
| CN101508469A (en) * | 2009-03-20 | 2009-08-19 | 云南锡业集团（控股）有限责任公司 | Synthesis of active ferrous sulphide and uses thereof |
| CN102489150A (en) * | 2011-12-13 | 2012-06-13 | 常州大学 | Preparation method for load type iron-based sulfureted hydrogen removal agent under room temperature |
| CN103974756A (en) * | 2011-12-15 | 2014-08-06 | 科莱恩公司 | Composition and process for mercury removal |
-
2016
- 2016-08-31 CN CN201610776789.9A patent/CN106378196A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5637033A (en) * | 1979-08-30 | 1981-04-10 | Dowa Mining Co Ltd | Substance for absorbing mercury in acidic exhaust gas |
| US4256707A (en) * | 1979-10-24 | 1981-03-17 | The United States Of America As Represented By The Secretary Of The Interior | Selective removal of mercury from cyanide solutions |
| CN101508469A (en) * | 2009-03-20 | 2009-08-19 | 云南锡业集团（控股）有限责任公司 | Synthesis of active ferrous sulphide and uses thereof |
| CN102489150A (en) * | 2011-12-13 | 2012-06-13 | 常州大学 | Preparation method for load type iron-based sulfureted hydrogen removal agent under room temperature |
| CN103974756A (en) * | 2011-12-15 | 2014-08-06 | 科莱恩公司 | Composition and process for mercury removal |
Non-Patent Citations (3)
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| 何杰等: "《工业催化》", 31 July 2014 * |
| 天津化工研究院: "《无机盐工业手册 下》", 31 January 2000 * |
| 朱洪法等: "《催化剂制备及应用技术》", 30 June 2011 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110756157A (en) * | 2019-11-08 | 2020-02-07 | 浙江大学 | Preparation and demercuration method of supported iron-based mercury adsorbent |
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