CN103521166A - Preparation method of copper-based mercury removing agent - Google Patents
Preparation method of copper-based mercury removing agent Download PDFInfo
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- CN103521166A CN103521166A CN201310498412.8A CN201310498412A CN103521166A CN 103521166 A CN103521166 A CN 103521166A CN 201310498412 A CN201310498412 A CN 201310498412A CN 103521166 A CN103521166 A CN 103521166A
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Abstract
The invention provides a preparation method of a copper-based mercury removing agent, belonging to the technical field of mercury removing agents. The preparation method comprises the following steps: (1) dissolving basic cupric carbonate into concentrated ammonia water or saturated ammonium bicarbonate solution or mixed solution of concentrated ammonia water and saturated ammonium bicarbonate, thus forming impregnation liquid; (2) impregnating a carrier in the impregnation liquid, taking out the impregnated and saturated carrier and draining or drying the carrier at 80-150 DEG C; (3) vulcanizing a mercury removing agent precursor, thus obtaining the copper-based mercury removing agent. The mercury removing agent prepared by the preparation method has the advantages of low production cost and high mercury removal accuracy.
Description
Technical field
The present invention relates to the preparation method that a kind of copper is mercury removal agent, belong to mercury removal agent technical field.
Background technology
In such as natural gas, liquefied petroleum gas, liquid hydrocarbon feeds (as naphtha, condensate and cut wet goods), all have a small amount of mercury, and the existence of mercury can cause following problem: aluminium heater generation amalgamation and being damaged; Make the expensive catalyst of downstream unit poisoning, greatly reduce its life-span; Pollute cask.In addition, mercury is one of most important toxicant in oil gas, and after oil gas burning, mercury can enter atmosphere and cause environmental pollution, and therefore above-mentioned material must remove mercury before using.
In prior art, normally used mercury removal agent is copper sulfide mercury removal agent.Such as american documentation literature US4094777, disclose a kind of absorbent of the presulfurization that comprises copper sulfide, the preparation method of this absorbent is as follows: by basic copper carbonate and refractory cement binding agent kneading, extrusion modling, obtains extrudate; By above-mentioned extrudate dry agent precursor that is absorbed at 80 ℃; Make again this absorbent precursor and contain sulphur compound as the gaseous stream of hydrogen sulfide contacts, by copper compound sulfuration, preparing the absorbent of this presulfurization.Above-mentioned technology is prepared in the process of demercuration absorbent and is adopted solid basic copper carbonate and solid refractory cement binding agent kneading and compacting, and the pore volume of the absorbent precursor of kneading and compacting is very low admittedly, in sulfidation, the surperficial basic copper carbonate that is present in absorbent precursor, be easy to contact with vulcanizing agent, form the active component copper sulfide of absorbent, and be present in the basic copper carbonate of absorbent precursor inside, because the pore volume of absorbent precursor is low, vulcanizing agent is difficult for entering the inside of absorbent precursor, the basic copper carbonate of this part is also just difficult for contacting with vulcanizing agent, and then cannot be formed by complete cure the active component of absorbent.The existence of the problems referred to above causes adopting that the pore volume of the demercuration absorbent that technology prepares is low, specific area is little, and the utilization rate of basic copper carbonate is low, increased the production cost of mercury absorbent, and demercuration precision is not high.
In order to solve the problems of the technologies described above, Chinese patent literature CN10 945700A also discloses a kind of copper sulfide mercury removal agent, the preparation method of this mercury removal agent is as follows: the composition kneading and compacting that can form copper compound, particulate support material and one or more binding agents of copper sulfide, prepare absorbent precursor, the wherein said copper compound that can form copper sulfide comprises cupric oxide, Kocide SD, basic copper carbonate; Dry this absorbent precursor material; Vulcanize this precursor material to form described absorbent.In above-mentioned patented technology, adopt after solid basic copper carbonate and solid carrier and solid binder kneading and compacting, then drying, vulcanize and prepare demercuration absorbent.Due to above-mentioned, admittedly in kneading process, added the carrier with pore structure, it can increase pore volume and the specific area of absorbent precursor to a certain extent, but because the duct of carrier in kneading process is admittedly very easily blocked, cause the demercuration precision of this demercuration absorbent not to be improved; In addition in kneading process, the structure of carrier is also easily destroyed, and then causes the intensity of demercuration absorbent low not high, and demercuration absorbent intensity is low, in use, can affect the service life of demercuration absorbent.
Because basic copper carbonate can directly vulcanize the active component for preparing mercury removal agent, therefore adopting basic copper carbonate is that raw material is while preparing mercury removal agent, conventionally the method that all adopts operating procedure simply to consolidate kneading and compacting is prepared mercury removal agent, and at kneading and compacting admittedly, easily cause the pore volume of mercury removal agent low, specific area is little, and then make the utilization rate of basic copper carbonate low, cause adopting the production cost of the mercury removal agent that the method prepares high, to inhale mercury precision low.
Summary of the invention
Technical problem to be solved by this invention is that the production cost of the mercury removal agent for preparing of available technology adopting basic copper carbonate is high, to inhale mercury precision low, and then the preparation method that a kind of production cost is low, inhale the mercury removal agent that mercury precision is high is provided.
In order to solve the problems of the technologies described above, the invention provides the preparation method that a kind of copper is mercury removal agent, comprise the steps:
(1) basic copper carbonate is dissolved in the mixed solution of ammoniacal liquor or unsaturated carbonate hydrogen ammonium salt solution or ammoniacal liquor and unsaturated carbonate hydrogen ammonium, forms maceration extract;
(2) by carrier impregnation in above-mentioned maceration extract, carrier after saturated dipping is taken out, drain or dry at 80 ~ 150 ℃, obtain mercury removal agent precursor;
(3) by above-mentioned mercury removal agent precursor sulfuration, obtaining copper is mercury removal agent.
In described step (1), basic copper carbonate is to be dissolved in completely in the mixed solution of ammoniacal liquor or unsaturated carbonate hydrogen ammonium salt solution or ammoniacal liquor and unsaturated carbonate hydrogen ammonium.
In described step (1), in maceration extract, the concentration of copper ion is 0.5 ~ 3.0mol/L.
In described step (2), the particle diameter of described carrier is that 1 ~ 5mm, pore volume are that 0.3 ~ 0.9 ml/g, specific area are 100 ~ 250 m
2/ g.
In described step (2), described carrier is any one or a few in activated carbon granule, alumina balls, molecular sieve spheres.
In described step (2), after the carrier after saturated dipping drains, then at 80 ~ 120 ℃ forced air drying 1 ~ 3h.
In described step (2), when the carrier after saturated dipping is dry at 80 ~ 150 ℃, described being dried under air blast condition carried out.
In described step (3), the vulcanizing agent of described sulfuration is any one in hydrogen sulfide, the sulfur content ammonium sulfide solution that is 1 ~ 9wt%.
In described step (3), the mercury removal agent after sulfuration is dry 1 ~ 12h under 80 ~ 150 ℃, air blast condition again.
In mass, in described mercury removal agent, the sulphur compound of copper and the ratio of carrier are (4 ~ 25): (75 ~ 96).
Copper of the present invention be mercury removal agent preparation method compared with prior art tool have the following advantages:
(1) copper of the present invention is in the preparation method of mercury removal agent, first basic copper carbonate is dissolved in the mixed solution of concentrated ammonia liquor or unsaturated carbonate hydrogen ammonium salt solution or concentrated ammonia liquor and unsaturated carbonate hydrogen ammonium, basic copper carbonate is dissolved in after above-mentioned solution, can form the maceration extract that contains cupric ammine complex, by carrier impregnation, after above-mentioned maceration extract, cupric ammine complex can be carried on inside and the surface of carrier equably, by the carrier drying after dipping, can make the moisture evaporation in carrier, thereby retain the pore volume of carrier, and copper compound uniform load is in carrier surfaces externally and internally, in sulfidation, because the pore volume of carrier is high, thereby make in sulfidation vulcanizing agent not only can with the copper compound generation vulcanization reaction of carrier surface, can also react with the copper compound of carrier inside, all generate the active component copper sulfide of mercury removal agent, in sulfidation of the present invention, quality in the copper compound of the load on carrier, the copper compound of > 99wt%, even the copper compound of 100wt% can be by complete cure, the utilization rate of active component is high, thereby reduced the production cost of mercury removal agent, also improved the demercuration precision of mercury removal agent simultaneously.Adopting copper of the present invention is that mercury removal agent that the preparation method of mercury removal agent prepares has advantages of that production cost is low, to inhale mercury precision high.
(2) copper of the present invention is the preparation method of mercury removal agent, and the concentration of further controlling copper ion in maceration extract is 0.5 ~ 3.0mol/L, and the particle diameter of simultaneously controlling described carrier is that 1 ~ 5mm, pore volume are that 0.3 ~ 0.9 ml/g, specific area are 100 ~ 250 m
2/ g, under the molar concentration of this copper ion, there is the carrier of above-mentioned specific physical property after saturated dipping, quality in cupric oxide, on carrier, the mass percent of copper compound can reach 4 ~ 25wt%, under the mass percent of this copper compound, the hole that can guarantee as far as possible dry rear carrier is not blocked, thereby guarantee that desulfurizing agent precursor has sufficiently high pore volume and specific area, make the copper compound of load on carrier can all be vulcanized the active component that forms mercury removal agent in sulfidation, also guaranteed that the mercury removal agent after sulfuration also has enough pore volumes simultaneously.Adopt the carrier of specific impregnation concentration of the present invention, specific physical property, the mercury removal agent preparing under given conditions, owing to having suitable pore volume, specific area and active component content, it can fully contact with treating demercuration raw material, and then improves the demercuration precision of mercury removal agent.
(3) copper of the present invention is in the preparation method of mercury removal agent, further be controlled under air blast condition the carrier after dipping is dried, air blast condition is easy to moisture evaporation, thereby the pore volume that retains carrier, further guarantee the copper compound sulfuration rate in mercury removal agent precursor, and then enter to improve the demercuration precision of raw material availability and mercury removal agent.
the specific embodiment
Below in conjunction with embodiment, the present invention is further described in detail, but is not limited to this.
embodiment 1
In the present embodiment, the preparation method of mercury removal agent is:
(1) 5.528g basic copper carbonate is dissolved in completely in the unsaturated carbonate hydrogen ammonium salt solution of 100ml, forms maceration extract;
(2) by the particle diameter of 50g, be that 1mm, pore volume are that 0.3ml/g, specific area are 100m
2the alumina balls carrier impregnation of/g, in above-mentioned maceration extract, is taken out the alumina balls carrier after saturated dipping, drains, and obtains mercury removal agent precursor;
(3) H at 1vol% by above-mentioned mercury removal agent precursor
2in S, sulfuration is to saturated, and obtaining copper is mercury removal agent A.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent A, the sulphur compound of copper and the ratio of carrier are 4:96.
embodiment 2
In the present embodiment, the preparation method of mercury removal agent is:
(1) basic copper carbonate of 11.056g is dissolved in completely in the ammoniacal liquor of 22wt% of 100ml, forms maceration extract;
(2) by the particle diameter of 50g, be that 3mm, pore volume are that 0.4ml/g, specific area are 120m
2the absorbent charcoal carrier of/g impregnated in above-mentioned maceration extract, and the absorbent charcoal carrier after saturated dipping is taken out, and at 80 ℃, dry 12h, obtains mercury removal agent precursor;
(3) by above-mentioned mercury removal agent precursor at 1 vol %H
2in S, sulfuration is to saturated, and obtaining copper is mercury removal agent B.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent B, the sulphur compound of copper and the ratio of carrier are 8:92
embodiment 3
In the present embodiment, the preparation method of mercury removal agent is:
(1) basic copper carbonate of 22.112g is dissolved in the ammoniacal liquor of 28wt% of 100ml, forms maceration extract;
(2) by the particle diameter of 50g, be that 5mm, pore volume are that 0.6ml/g, specific area are 180m
2the absorbent charcoal carrier of/g impregnated in above-mentioned maceration extract, and the absorbent charcoal carrier after saturated dipping is taken out, and at 120 ℃, dry 6h, obtains mercury removal agent precursor;
(3) by above-mentioned mercury removal agent precursor at 1 vol %H
2in S, sulfuration is to saturated, and obtaining copper is mercury removal agent C.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent C, the sulphur compound of copper and the ratio of carrier are 14:86.
embodiment 4
In the present embodiment, the preparation method of mercury removal agent is:
(1) basic copper carbonate of 33.15g is dissolved in completely in the ammoniacal liquor of 28wt% of 100ml, forms maceration extract;
(2) by the particle diameter of 50g, be that 1 ~ 5mm, pore volume are that 0.7 ~ 0.9ml/g, specific area are 250m
2the molecular sieve spheres carrier impregnation of/g, in above-mentioned maceration extract, is taken out the molecular sieve spheres carrier after saturated dipping, and at 150 ℃, dry 1h, obtains mercury removal agent precursor;
(3) above-mentioned mercury removal agent precursor be impregnated in the ammonium sulfide solution that the sulfur content of 90ml is 8wt%, dipping 2h, is taken out, and drains 2h, and after 90 ℃ of dry 3h, obtaining copper is mercury removal agent D.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent D, the sulphur compound of copper and the ratio of carrier are 25:75.
embodiment 5
In the present embodiment, the preparation method of mercury removal agent is:
(1) basic copper carbonate of 20g is dissolved in completely in the ammoniacal liquor of 90ml and the mixed solution of carbonic hydroammonium, wherein the ratio of the addition of the carbonic hydroammonium in the ammonia in ammoniacal liquor described in mixed solution and described unsaturated carbonate hydrogen ammonium salt solution is any ratio, in the present embodiment, select 8g carbonic hydroammonium to be dissolved in the 14wt% ammoniacal liquor of 90ml, form mixed solution;
(2) by the particle diameter of 50g, be that 2mm, pore volume are that 0.5ml/g, specific area are 150m
2the molecular sieve spheres of/g impregnated in above-mentioned maceration extract, after dipping 1h, the molecular sieve carrier after saturated dipping is taken out, and drains 0.5h, is dried after 3h, then is dried 3h under 90 ℃ of air blast conditions under 120 ℃ of air blast conditions, obtains mercury removal agent precursor;
(3) above-mentioned mercury removal agent precursor be impregnated in the ammonium sulfide solution that the sulfur content of 90ml is 9wt%, dipping, to saturated, is taken out, drains 2h, under 90 ℃ of air blast conditions after dry 3h, then under 120 ℃ of air blast conditions, is dried that to obtain copper after 3h be mercury removal agent E.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent E, the sulphur compound of copper and the ratio of carrier are 15:85.
embodiment 6
In the present embodiment, the preparation method of mercury removal agent is:
(1) 20g basic copper carbonate is dissolved in the 28wt% concentrated ammonia liquor of 90ml, forms maceration extract;
(2) by the particle diameter of 50g, be that 4mm, pore volume are that 0.7ml/g, specific area are 200m
2the molecular sieve spheres carrier impregnation of/g is in above-mentioned maceration extract, and the dipping that reaches capacity after dipping 1h, takes out the molecular sieve spheres carrier after saturated dipping, drains 0.5h, under 80 ℃ of air blast conditions, after dry 3h, obtains mercury removal agent precursor;
(3) above-mentioned mercury removal agent precursor be impregnated in the ammonium sulfide solution that the sulfur content of 90ml is 1%, dipping, to saturated, is taken out, drains 3h, and the mercury removal agent obtaining is dried and obtains copper after 12h under 80 ℃ of air blast conditions is mercury removal agent F.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent F, the sulphur compound of copper and the ratio of carrier are 12:88.
embodiment 7
In the present embodiment, the preparation method of mercury removal agent is:
(1) 20g basic copper carbonate is dissolved in the ammoniacal liquor of 90ml and the mixed solution of carbonic hydroammonium, wherein the ratio of the addition of the carbonic hydroammonium in the ammonia in ammoniacal liquor described in mixed solution and described unsaturated carbonate hydrogen ammonium salt solution is any ratio, in the present embodiment, select 20g carbonic hydroammonium to be dissolved in the 10wt% ammoniacal liquor of 90ml, form mixed solution;
(2) by the particle diameter of 50g, be that 3 ~ 5mm, pore volume are that 0.6 ~ 0.8ml/g, specific area are 230m
2the molecular sieve spheres carrier impregnation of/g is in above-mentioned maceration extract, and the dipping that reaches capacity after dipping 1h, takes out the molecular sieve spheres carrier after saturated dipping, drain 0.5h, under 90 ℃ of air blast conditions, be dried after 3h, then be dried 3h under 120 ℃ of air blast conditions, obtain mercury removal agent precursor;
(3) above-mentioned mercury removal agent precursor be impregnated in the ammonium sulfide solution that the sulfur content of 100ml is 5wt%, dipping, to saturated, is taken out, drains 3h, obtains mercury removal agent and under 150 ℃ of air blast conditions, is dried that to obtain copper after 1h be mercury removal agent G again.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent G, the sulphur compound of copper and the ratio of carrier are 13:87
embodiment 8
In the present embodiment, the preparation method of mercury removal agent is:
(1) 40g basic copper carbonate is dissolved in the 28wt% ammoniacal liquor of 90ml and the mixed solution of unsaturated carbonate hydrogen ammonium, wherein the ratio of the addition of the carbonic hydroammonium in the ammonia in ammoniacal liquor described in mixed solution and described unsaturated carbonate hydrogen ammonium salt solution is any ratio, in the present embodiment, select 8g carbonic hydroammonium to be dissolved in the 28wt% ammoniacal liquor of 90ml, form mixed solution;
(2) by the particle diameter of 50g, be that 6mm, pore volume are that 1.0ml/g, specific area are 300m
2the molecular sieve spheres carrier impregnation of/g in above-mentioned maceration extract, flood saturated after, molecular sieve spheres carrier after saturated dipping is taken out, drain 3h, obtain mercury removal agent precursor;
(3) above-mentioned mercury removal agent precursor be impregnated in the ammonium sulfide solution that the sulfur content of 100ml is 9wt%, dipping, to saturated, is taken out, drains 3h, obtains mercury removal agent and under 150 ℃ of air blast conditions, is dried that to obtain copper after 1h be mercury removal agent H again.
According to " GBT 3884.1-2012 copper concentrate chemical analysis method part 1: the mensuration iodimetric titration of copper amount " and " GBT 3884.3-2012 copper concentrate chemical analysis method the 3rd part: gravimetry method and the burning-titration of sulfur content " test, in mercury removal agent H, the sulphur compound of copper and the ratio of carrier are 31:69.
comparative example
The preparation method of the mercury removal agent of recording in the list of references CN101945700A that comparative example adopts background technology of the present invention partly to quote prepares mercury removal agent, specifically comprises the steps:
(1) get the particulate material that particle diameter that the quick-drying basic copper carbonate of 25g, 75g hibbsite, 14g binding agent kneading, moulding obtain is 1 ~ 5mm, wherein said binding agent comprises the aluminous cement that 10 parts of CaO content are about 40wt% and adds 4 parts of attapulgite clay;
(2) above-mentioned particulate material is dried after 2h at ambient temperature, then at 105 ℃ of air drying 16h, obtaining grain diameter is the mercury removal agent precursor of 1 ~ 5mm;
(3) by described mercury removal agent precursor at 1%H
2in S, sulfuration, to saturated, obtains active mercury removal agent.
activity rating example
The mercury removal agent that embodiment 1 ~ 8 and comparative example are prepared averages compression strength, specific area, pore volume and demercuration active testing, and method of testing is as follows, and test result is as shown in table 1.
Mean compressive strength: adopt " mensuration of HG/T 2782-2011 chemical fertilizer catalyst particle anti-crushing power " method.
Pore volume, specific area: adopt " pore volume and pore-size distribution that RIPP 151-90 nitrogen adsorption capacity method is measured catalyst " and " GB-T 19587-2004 gas absorption BET method is measured solid matter specific area " method.
Demercuration activity rating adopts gas phase Solid Bed dynamic evaluation approach, specific as follows: to use simple and easy mercury generator to the mercury of allocating 5 ~ 35 μ g/L in carrier gas into, pass through solid-bed reactor, tail gas can adopt " the mensuration Cold Atomic Fluorescent Mercury AAS of GBT 16781.2-1997 Hg in natural gas content " to measure, when outlet mercury concentration surpasses 10 μ g/m continuous three times
3in time, is thought and penetrates.The mercury removal agent that will give up takes off, and after mixing, adopts " the mensuration cold atomic absorbent spectrophotometry of GBT 17136-1997 soil quality total mercury " to carry out mercury and holds mensuration.
The compression strength of table 1 mercury removal agent, specific area, pore volume and demercuration active testing result
| Sample title | A | B | C | D | E | F | G | H | Comparative example |
| Compression strength, N/ grain | 151 | 155 | 153 | 160 | 150 | 161 | 156 | 163 | 133 |
| Specific area, m 2/g | 123 | 120 | 116 | 110 | 115 | 119 | 117 | 90 | 59.2 |
| Pore volume (ml/g) | 0.40 | 0.30 | 0.25 | 0.20 | 0.25 | 0.27 | 0.26 | 0.17 | 0.12 |
| Mercury holds (%) | 1.0 | 3.2 | 4.4 | 4.1 | 5.3 | 5.1 | 4.8 | 3.1 | 2.1 |
From above-mentioned test result, copper of the present invention is that the compression strength of the mercury removal agent for preparing of mercury removal agent preparation method can reach 123m up to 163N/ grain, specific area
2/ g, pore volume maximum can remain on 0.40ml/g, the mercury of demercuration holds can be up to 5.3%, the correlated performance of the mercury removal agent that the preparation method who is far superior to adopt in comparative example prepares, illustrates that copper of the present invention is that mercury removal agent preparation method has remarkable advantage.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments, and the apparent variation of being extended out thus or change are still among the protection domain in the invention claim.
Claims (10)
1. copper is a preparation method for mercury removal agent, comprises the steps:
(1) basic copper carbonate is dissolved in the mixed solution of ammoniacal liquor or unsaturated carbonate hydrogen ammonium salt solution or ammoniacal liquor and unsaturated carbonate hydrogen ammonium, forms maceration extract;
(2) by carrier impregnation in above-mentioned maceration extract, carrier after saturated dipping is taken out, drain or dry at 80 ~ 150 ℃, obtain mercury removal agent precursor;
(3) by above-mentioned mercury removal agent precursor sulfuration, obtaining copper is mercury removal agent.
2. copper is the preparation method of mercury removal agent according to claim 1, it is characterized in that, in described step (1), basic copper carbonate is to be dissolved in completely in the mixed solution of ammoniacal liquor or unsaturated carbonate hydrogen ammonium salt solution or ammoniacal liquor and unsaturated carbonate hydrogen ammonium.
3. according to copper described in claim 1 or 2, be the preparation method of mercury removal agent, it is characterized in that, in described step (1), in maceration extract, the concentration of copper ion is 0.5 ~ 3.0mol/L.
4. according to copper described in claim 1 or 2 or 3, be the preparation method of mercury removal agent, it is characterized in that, in described step (2), the particle diameter of described carrier is that 1 ~ 5mm, pore volume are that 0.3 ~ 0.9 ml/g, specific area are 100 ~ 250 m
2/ g.
5. the preparation method who is mercury removal agent according to the arbitrary described copper of claim 1 ~ 4, is characterized in that, in described step (2), described carrier is any one or a few in activated carbon granule, alumina balls, molecular sieve spheres.
6. the preparation method who is mercury removal agent according to the arbitrary described copper of claim 1 ~ 5, is characterized in that, in described step (2), after the carrier after saturated dipping drains, then at 80 ~ 120 ℃ forced air drying 1 ~ 3h.
7. the preparation method who is mercury removal agent according to the arbitrary described copper of claim 1 ~ 6, is characterized in that, in described step (2), when the carrier after saturated dipping is dry at 80 ~ 150 ℃, described being dried under air blast condition carried out.
8. the preparation method who is mercury removal agent according to the arbitrary described copper of claim 1 ~ 7, is characterized in that, in described step (3), the vulcanizing agent of described sulfuration is any one in hydrogen sulfide, the sulfur content ammonium sulfide solution that is 1 ~ 9wt%.
9. the preparation method who is mercury removal agent according to the arbitrary described copper of claim 1 ~ 8, is characterized in that, in described step (3), the mercury removal agent after sulfuration is dry 1 ~ 12h under 80 ~ 150 ℃, air blast condition again.
10. the mercury removal agent that the preparation method that the arbitrary described copper of claim 1 ~ 9 is mercury removal agent prepares, is characterized in that, in mass, in described mercury removal agent, the sulphur compound of copper and carrier mass ratio are (4 ~ 25): (75 ~ 96).
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Application publication date: 20140122 |