CN104785278A - Mercury-removing catalyst and preparation method thereof - Google Patents
Mercury-removing catalyst and preparation method thereof Download PDFInfo
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- CN104785278A CN104785278A CN201510132500.5A CN201510132500A CN104785278A CN 104785278 A CN104785278 A CN 104785278A CN 201510132500 A CN201510132500 A CN 201510132500A CN 104785278 A CN104785278 A CN 104785278A
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Abstract
The invention relates to a mercury-removing catalyst and a preparation method thereof. The mercury-removing catalyst is prepared from the following constituents based on mass percent: 50-90% of aluminum oxide, 2-50% of copper sulfide, and 2-15% of an adsorption auxiliary agent. The preparation method comprises the following steps: A. taking a certain amount of aluminum oxide powder, adding the adsorption auxiliary agent into the powder, fully mixing the aluminum oxide powder with the adsorption auxiliary agent, pressing the mixture into small balls with the diameter of 2 mm, and dipping the small balls into a metal salt solution to perform saturated absorption; B. performing a hybrid reaction on the small balls prepared in the step A with sulfide; C. washing with deionized water; D. using a drying oven to dry the washed small balls to obtain the finished product. The mercury-removing catalyst disclosed by the invention is convenient to prepare, high in strength of the catalyst, capable of adjusting the adsorption mercury capacity and solving the problem that the element mercury removing performance of the activated carbon is poor; moreover, the service life is as long as two years.
Description
Technical field
The present invention relates to a kind of demercuration catalyst and preparation method thereof.
Background technology
The discharge of heavy metal (as Hg, Ni, Cr etc.) becomes day by day serious environmental problem due to meeting harm humans health.Mercury is a kind of element concerned especially, because in coal and municipal solid waste combustion process, the most of mercury be present in coal and MSW are transformed into gaseous state due to its high volatility.Mercury is once enter air, and it stored for a long timely can cause long-term pollution problem in environment.In addition, many data prove that mercury can transmit and understand bioaccumulation in food chain, need the strict mercury emissions controlling coal-fired power plant and other mercury source.
Along with country is to the attention of environmental protection cause, the technology of existing control mercury emissions adds in active carbon by the sulphur flooding different shape, because sulphur is deposited on activated carbon surface, therefore some shortcomings can be there are in final product or method, as: make the uniformity of sulphur on carbon surface have problem due to the inhomogeneity of carbon surface, the content of sulphur in charcoal is restricted; After carbon surface forms carbon-sulphur complex, hole mouth obviously reduces, and causes surface area to decline; Chemical interaction between sulphur and carbon can be very weak; Owing to competing with sulphur on carbon surface active site, be restricted adding of other additive; Adsorption of Mercury capacity is few, catalysis intensity difference; Service life is no more than 5 months, and the quality of activated carbon of different batches cannot ensure identical.And high-efficiency desulfurization catalyst, demercuration catalyst and extraordinary catalyst, major technology bottleneck is that catalyst activity is not high, and stability is bad.
Summary of the invention
The object of this invention is to provide a kind of prepare simple, catalysis intensity is high, can solve active carbon removes demercuration catalyst of the problems such as element mercury poor performance and different batches quality of activated carbon cannot ensure and preparation method thereof.
The object of the invention is to realize as follows:
A kind of demercuration catalyst, comprise mass percent be 50% ~ 90% aluminium oxide and mass percent be the copper sulfide of 2% ~ 50%.
Technique scheme also comprise mass percent be 2% ~ 15% help adsorbent.
The mass percent of aluminium oxide described in technique scheme is 70% ~ 90%, and more excellent scheme is 75% ~ 80%.The mass percent of copper sulfide described in technique scheme is 5% ~ 30%, and more excellent scheme is 8% ~ 20%
3, a preparation method for demercuration catalyst, is characterized in that, concrete steps comprise:
A, to get alumina powder some, add and help adsorbent fully to mix, be pressed into the bead that diameter is 2mm, and immerse saturated absorption in copper chloride solution;
B, by the bead made in steps A and hydrogen sulfide hybrid reaction;
C, use deionized water impurity elimination;
D, obtain finished product with oven drying.
Described in technique scheme, step B is specially:
A, the bead made in steps A put into the dry 4h of baking oven of 120 DEG C;
B, the bead after process in step a to be loaded in glass reaction tube, and the hydrogen sulfide gas passed in glass reaction tube, make copper chloride generate copper sulfide, and take out bead.
Described in technique scheme, step B is specially: immerse in hydrogen sulfide solution by the bead made in steps A, takes out bead after room temperature to 100 DEG C reaction 24h.
Described in technique scheme, step D is specially: obtain finished product with the oven drying 4h of 120 DEG C.
Described in technique scheme, step D is specially: obtain oven drying 8h with 110 DEG C and obtain finished product.
Alumina powder described in technique scheme is α-Al2O3 powder or β-Al2O3 powder or γ-Al2O3 powder.
Adsorbent is helped to be the carclazyte of loose structure or clay or nano kaoline or coconut husk Powdered Activated Carbon described in technique scheme.
Hydrogen sulfide described in technique scheme can substitute with divalent metal sulfide or transient metal sulfide.
Adsorbent is helped to be the carclazyte of loose structure or clay or nano kaoline or coconut husk Powdered Activated Carbon etc. described in technique scheme.
Advantage of the present invention:
(1) the present invention has that preparation is simple, catalyst strength is high, and Adsorption of Mercury capacity is many, solves the problem that active carbon removes element mercury poor performance, and reaches 2 years service life.
(2) the present invention can remove mercury salt, mercury compound and element mercury, and removes better performances.
detailed description of the invention:
(embodiment 1)
Get α-Al
2o
3100 grams, powder and nano kaoline 10 grams, fully mix, be pressed into the bead that diameter is two millimeters.Get 0.1 mole of copper chloride and be mixed with solution, this solution is made all to suck in above-mentioned bead, by this bead dry 4h in 120 DEG C of baking ovens, then load in glass reaction tube, in glass reaction tube, pass into the hydrogen sulfide gas of 60 DEG C, make copper chloride generate copper sulfide, take out, wash away sodium chloride with deionized water, in 120 DEG C of baking ovens, dry 4h obtains finished product demercuration catalyst.Demercuration catalyst is loaded in demercuration reactor, pass in reactor 50 DEG C containing mercury element natural gas, this demercuration catalyst can suck the mercury 3.5 grams in natural gas.
(embodiment 2)
Get β-Al
2o
3100 grams, powder and coconut husk Powdered Activated Carbon 10 grams, fully mix, be pressed into the bead that diameter is two millimeters.Get 0.1 mole of copper chloride and be mixed with solution, this solution is made all to suck in above-mentioned bead, by this bead dry 4h in 120 DEG C of baking ovens, then load in glass reaction tube, in glass reaction tube, pass into the hydrogen sulfide gas of 60 DEG C, make copper chloride generate copper sulfide, take out, wash away sodium chloride with deionized water, in 120 DEG C of baking ovens, dry 4h obtains finished product demercuration catalyst.Demercuration catalyst is loaded in demercuration reactor, pass in reactor 50 DEG C containing mercury element natural gas, this demercuration catalyst can suck the mercury 3.6 grams in natural gas.
(embodiment 3)
Get γ-Al
2o
3100 grams, powder and coconut husk Powdered Activated Carbon 10 grams, fully mix, be pressed into the bead that diameter is two millimeters.Get 0.1 mole of copper chloride and be mixed with solution, this solution is made all to suck in above-mentioned bead, by this bead dry 4h in 120 DEG C of baking ovens, then load in glass reaction tube, in glass reaction tube, pass into the hydrogen sulfide gas of 60 DEG C, make copper chloride generate copper sulfide, take out, wash away sodium chloride with deionized water, in 120 DEG C of baking ovens, dry 4h obtains finished product demercuration catalyst.Demercuration catalyst is loaded in demercuration reactor, pass in reactor 50 DEG C containing mercury element natural gas, this demercuration catalyst can suck the mercury 3.4 grams in natural gas.
(embodiment 4)
Soak the bead 100 grams of copper chloride solution in Example 1, separately get 0.2 moles of hydrogen sulfide wiring solution-forming.Immersed by bead in sulfide solution, room temperature, to 100 DEG C of reaction 24h, is taken out, is washed away impurity, obtain finished product demercuration catalyst with 110 DEG C of oven drying 8h with deionized water.Demercuration catalyst is loaded in demercuration reactor, pass in reactor 50 DEG C containing mercury element natural gas, this demercuration catalyst can suck the mercury 3.3 grams in natural gas.
Above-described specific embodiment; object of the present invention, technical scheme and beneficial effect are further described; be understood that; the foregoing is only specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any amendment made, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a demercuration catalyst, is characterized in that: comprise mass percent be 50% ~ 90% aluminium oxide and mass percent be the copper sulfide of 2% ~ 50%.
2. demercuration catalyst according to claim 1, is characterized in that: also comprise mass percent be 2% ~ 15% help adsorbent.
3. a preparation method for demercuration catalyst, is characterized in that, concrete steps comprise:
A, to get alumina powder some, add and help adsorbent fully to mix, be pressed into the bead that diameter is 2mm, and immerse saturated absorption in copper chloride solution;
B, by the bead made in steps A and hydrogen sulfide hybrid reaction;
C, to wash with deionized water;
D, obtain finished product with oven drying.
4. the preparation method of a kind of demercuration catalyst according to claim 3, is characterized in that, described step B is specially:
A, the bead made in steps A put into the dry 4h of baking oven of 120 DEG C;
B, the bead after process in step a to be loaded in glass reaction tube, and the hydrogen sulfide gas passed in glass reaction tube, make copper chloride generate copper sulfide, and take out bead.
5. the preparation method of a kind of demercuration catalyst according to claim 3, is characterized in that, described step B is specially: the bead made in steps A is immersed saturated absorption in copper chloride solution, takes out bead after room temperature to 100 DEG C reaction 24h.
6. the preparation method of a kind of demercuration catalyst according to claim 4, is characterized in that, described step D is specially: obtain finished product with the oven drying 4h of 120 DEG C.
7. the preparation method of a kind of demercuration catalyst according to claim 5, is characterized in that, described step D is specially: obtain oven drying 8h with 110 DEG C and obtain finished product.
8. the preparation method of a kind of demercuration catalyst according to claim 6 or 7, is characterized in that, described alumina powder is α-Al
2o
3powder or β-Al
2o
3powder or γ-Al
2o
3powder.
9. the preparation method of a kind of demercuration catalyst according to claim 3, is characterized in that, described in help adsorbent to be the carclazyte of loose structure or clay or nano kaoline or coconut husk Powdered Activated Carbon.
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| CN201510132500.5A CN104785278A (en) | 2015-03-25 | 2015-03-25 | Mercury-removing catalyst and preparation method thereof |
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| CN201510132500.5A CN104785278A (en) | 2015-03-25 | 2015-03-25 | Mercury-removing catalyst and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925297A (en) * | 2016-09-08 | 2017-07-07 | 江苏常州酞青新材料科技有限公司 | A kind of demercuration catalyst and preparation method thereof |
| CN107149922A (en) * | 2016-03-03 | 2017-09-12 | 中国石油大学(北京) | A kind of bimetallic sulfide demercuration adsorbent and its preparation method and application |
| CN107486133A (en) * | 2017-09-12 | 2017-12-19 | 常州大学 | A kind of natural gas mercury-removing adsorbent and preparation method |
| CN108404849A (en) * | 2018-04-18 | 2018-08-17 | 常州大学 | A kind of natural gas mercury-removing adsorbent and preparation method thereof |
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|---|---|---|---|---|
| US4094777A (en) * | 1975-12-18 | 1978-06-13 | Institut Francais Du Petrole | Process for removing mercury from a gas or a liquid by absorption on a copper sulfide containing solid mass |
| CN1037466A (en) * | 1988-03-10 | 1989-11-29 | 法国石油公司 | The method of from hydrocarbon, removing mercury and may also have arsenic |
| CN1062301A (en) * | 1990-10-30 | 1992-07-01 | 法国石油公司 | In the presence of the trapping agent of mercury and/or arsenic, remove the method for mercury and arsenic in the fluid |
| CN101945700A (en) * | 2008-02-15 | 2011-01-12 | 约翰森·马瑟公开有限公司 | Absorbent |
| CN102574097A (en) * | 2009-08-17 | 2012-07-11 | 约翰森·马瑟公开有限公司 | Sorbent |
| CN104105536A (en) * | 2012-02-06 | 2014-10-15 | 环球油品公司 | Method of removing mercury from fluid stream using high capacity copper adsorbents |
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2015
- 2015-03-25 CN CN201510132500.5A patent/CN104785278A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4094777A (en) * | 1975-12-18 | 1978-06-13 | Institut Francais Du Petrole | Process for removing mercury from a gas or a liquid by absorption on a copper sulfide containing solid mass |
| CN1037466A (en) * | 1988-03-10 | 1989-11-29 | 法国石油公司 | The method of from hydrocarbon, removing mercury and may also have arsenic |
| CN1062301A (en) * | 1990-10-30 | 1992-07-01 | 法国石油公司 | In the presence of the trapping agent of mercury and/or arsenic, remove the method for mercury and arsenic in the fluid |
| CN101945700A (en) * | 2008-02-15 | 2011-01-12 | 约翰森·马瑟公开有限公司 | Absorbent |
| CN102574097A (en) * | 2009-08-17 | 2012-07-11 | 约翰森·马瑟公开有限公司 | Sorbent |
| CN104105536A (en) * | 2012-02-06 | 2014-10-15 | 环球油品公司 | Method of removing mercury from fluid stream using high capacity copper adsorbents |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107149922A (en) * | 2016-03-03 | 2017-09-12 | 中国石油大学(北京) | A kind of bimetallic sulfide demercuration adsorbent and its preparation method and application |
| CN107149922B (en) * | 2016-03-03 | 2019-09-17 | 中国石油大学(北京) | A kind of bimetallic sulfide demercuration adsorbent and its preparation method and application |
| CN106925297A (en) * | 2016-09-08 | 2017-07-07 | 江苏常州酞青新材料科技有限公司 | A kind of demercuration catalyst and preparation method thereof |
| CN107486133A (en) * | 2017-09-12 | 2017-12-19 | 常州大学 | A kind of natural gas mercury-removing adsorbent and preparation method |
| CN107486133B (en) * | 2017-09-12 | 2019-12-31 | 常州大学 | Natural gas demercuration adsorbent and preparation method thereof |
| CN108404849A (en) * | 2018-04-18 | 2018-08-17 | 常州大学 | A kind of natural gas mercury-removing adsorbent and preparation method thereof |
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Application publication date: 20150722 |
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