CN1273567C - Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent - Google Patents
Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent Download PDFInfo
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- CN1273567C CN1273567C CN 02137653 CN02137653A CN1273567C CN 1273567 C CN1273567 C CN 1273567C CN 02137653 CN02137653 CN 02137653 CN 02137653 A CN02137653 A CN 02137653A CN 1273567 C CN1273567 C CN 1273567C
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- transition metal
- containing hydrocarbon
- dearsenic agent
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- oxide
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Abstract
The present invention relates to a method for eliminating arsenic in an alkyne containing hydrocarbon, which comprises: the alkyne containing hydrocarbon with 0.1 to 50 vol% of added hydrogen passes through a fixed bed filled with a dearsenization agent at the temperature of 0 to 150DEG C at the pressure of 0.01 to 3MPa, and the gas space velocity is lower than or equal to 4000 h<-1>; the dearsenization agent is prepared from a carrier, at least one transitional metal and/or at least one transition metal oxide, wherein the transitional metals are selected from an IB group, an IIB group, a VB group, a VIB group, a VIIB group and a VIII group in a periodic table of elements; the transitional metals and/or the transition metal oxides are loaded on the carrier. In the method, a chemical reaction among alkyne and the metals and/or the metal oxides in the dearsenization agent can be inhibited. The present invention has the advantages of high activity of the dearsenization agent, large dearsenization capacity, low preparation cost and high adaptability. The present invention is suitable for the dearsenization of the alkyne containing hydrocarbon.
Description
Technical field
The present invention relates to a kind of method and dearsenic agent that removes arsenic in the acetylene-containing hydrocarbon.
Background technology
As everyone knows, harmful component that may contain many trace in the petroleum crude oil, usually the form with organic clement compound exists, these organic clement compounds are subjected to the influence of these organic clement compounds and cause permanent poisoning and can make that the poisoning of catalyst, particularly selective hydrogenation catalyst used in the petroleum refining process are easier.Though in alkene such as ethene, the third rare production, crude oil is through behind distillation, underpressure distillation and the catalytic pyrolysis, most elements organic compound has wherein all obtained removing preferably, but arsenic element but generates some volatile compounds easily, mainly exist with forms such as hydrogen arsenide, monomethyl arsine, dimethyl arsine, trimethylammonium arsine, tributyl arsines, its content is mostly 10
-6～10
-7In the scope, the catalyzer of subsequent process such as hydrogenation catalyst and olefin polymerization catalysis are had serious permanent toxication, therefore must before subsequent disposal, adopt suitable arsenic removing method that above-mentioned arsenide is removed.
The catalyst type that is used for dearsenification is a lot, and generally the difference according to the catalyst activity component is divided into catalyzer three classes such as Cu-series catalyst, nickel catalyst, noble metal catalyst.
With gac etc. is that the copper based de-arsenic catalyst of carrier has good dearsenification effect to volatile arsenide, and the arsenic capacity is bigger, and the dearsenification temperature is lower, is adapted to the dearsenification before the olefinic polymerization especially.In the prior art, U.S. Pat 5169516 has been described a kind of with CuO/ZnO/Al
2O
3Dearsenification process for dearsenic agent.The hydrocarbon compound that uses the dearsenification process of this catalyzer to be applicable to contain organic sulfide such as the dearsenification of petroleum naphtha.Its principal feature is that the content of plumbous oxide is controlled at below 20% in the dearsenic agent, helps suppressing the absorption to organic sulfide, improves the dearsenification performance.
Chinese patent CN1278523A has also described a kind of arsenic removal catalyst based on CuO, this catalyzer can remove the trace arsenide in gas phase or the hydrocarbon liquid phase at normal temperatures, have the degree of depth of purification height, long service life, dearsenification characteristics capacious, arsenide content can be reduced to below the 1ppb in the hydrocarbon of purification back.
Employing is suitable for the hydrodearsenication process of liquid hydrocarbon such as crude oil normal pressure cut such as petroleum naphtha and natural gas condensate under the hydro condition based on the nickel based de-arsenic catalyst of Ni+NiO or Ni-Mo.Chinese patent CN1021340C disclose a kind of from liquid state hydrocarbon polymer or the mixture of hydrocarbon polymer remove the method for dephosphorization and arsenic, be that above-mentioned hydrocarbon polymer is contacted with the catalyzer that contains 50% metal state nickel at least with hydrogen, working temperature is 110～280 ℃, and operating pressure is 1～100 crust.
Chinese patent CN1021409C is under the situation that hydrogen exists, with hydrocarbon with a kind of be that the catalyzer of a kind of metal in nickel, cobalt, iron and the palladium contacts at least, can be except that mercury and the arsenic in the dealkylation.
Chinese patent CN1040452C discloses a kind of arsenic removing method in the petroleum naphtha treating process, and this method makes spent hydroprocessing catalyst, and reaction pressure is 1.0～8.0MPa, and temperature is controlled at 300～450 ℃, and the reaction solution air speed is 1.0～8.0h
-1, the reactive hydrogen oil ratio is 60～500, hydrogen supply gas hydrogen content is 35～100% (V), and arsenic content is reduced to below the 5ppb.
Chinese patent CN1043151C discloses dearsenic catalyst of a kind of liquid hydrocarbon and preparation method thereof, this catalyzer is made up of nickeliferous active ingredient and aluminum oxide, catalyzer feeds the gas mixture reduction of at least 10% hydrogen under 250～450 ℃ of conditions, feeding hydrogen down at 300 ℃ again activates, catalyst activated is carried out dearsenification to containing the arsenic liquid hydrocarbon under 80～250 ℃, the arsenic content of liquid hydrocarbon can be reduced to below the 5ppb.
The unsaturated multibinding compound of carbon containing carbon, selective hydrogenation generation monoolefine as alkynes and diolefine is that the important process process that device is produced alkene is separated in refining, along with refining is separated the raw material composition and is become increasingly complex, to bring more volatility arsenide in the refining hydrolysis products, therefore, the refining that contains alkynes and diolefine separates that the dearsenification process is the key that is related to follow-up noble metal hydrogenation catalyst life-span length before the hydrogenation of product.Since alkynes easily with the stable metal acetylide of element interaction generation such as Cu, Ni is that dearsenic catalyst only just has activity under hot conditions, and the cost of catalyzer is high again, so above-mentioned dearsenic catalyst and arsenic removing method also are not suitable for the dearsenification of acetylene-containing hydrocarbon.Although existing many dearsenification processes are developed, there is no indication the report of existing acetylene-containing hydrocarbon arsenic removing method.
Summary of the invention
The purpose of this invention is to provide a kind of method and dearsenic agent that removes arsenic in the acetylene-containing hydrocarbon, this method has overcome the shortcoming that aforesaid method is not suitable for the acetylene-containing hydrocarbon dearsenification, the acetylene-containing hydrocarbon that generally can be 100～1000ppb with arsenic content is removed to below the 10ppb, preferably can be removed to below the 5ppb.
The present invention realizes like this.Of the present invention remove in the acetylene-containing hydrocarbon method of arsenic be with acetylene-containing hydrocarbon by the fixed bed of dearsenic agent is housed, its temperature is controlled at 0～150 ℃, pressure is 0.01～3MPa, gas space velocity≤4000h
-1, added percent by volume in the described acetylene-containing hydrocarbon and be 0.1～50% hydrogen.
Method of the present invention is suitable for removing acetylene-containing hydrocarbon and is and contains at least a gaseous state or liquid hydrocarbon mixture in the following alkynes of 6 carbon atoms and alkane, alkene, the diolefine.Be more suitable for gaseous state hydrocarbon mixture at least a in containing propine and propane, propylene, propadiene.
According to the present invention, import acetylene-containing hydrocarbon material contains the hydrogen of volume ratio 0.1～50.0%, the adding of hydrogen helps the catalyst activity component metals and keeps going back ortho states, and the excessive maintenance that is unfavorable for the transition metal oxide oxidation state of hydrogen content finally influences the dearsenification performance of dearsenic agent.In acetylene-containing hydrocarbon, add the generation that an amount of hydrogen also helps preventing the transition metal acetylide.Therefore adding an amount of hydrogen in the dearsenification material is one of principal character of the present invention to improve the dearsenification performance.
Dearsenification process of the present invention is carried out in the fixed-bed reactor that the dearsenic agent that the present invention selects for use is housed.With the dearsenification temperature of acetylene-containing hydrocarbon between 0～150 ℃, preferred 50～100 ℃; Dearsenification pressure between 0.01～3.0MPa, preferred 0.1～1.0MPa; Gas space velocity≤the 4000h of dearsenification
-1, preferred≤2000h
-1
According to the present invention, the dearsenic agent carrier is a kind of mixed type carrier to three kinds of compositions that is selected from gac, aluminum oxide, magnesium oxide, zinc oxide, cupric oxide, chromic oxide, zirconium white, silicon-dioxide, titanium dioxide, sieve and silica-sesquioxide, aluminum fluoride, magnesium fluoride, chromium fluoride, ZSM-5 molecular sieve, 3A molecular sieve, 4A molecular sieve, MCM-41 molecular sieve, the USY molecular sieve, and should contain the aluminum oxide of 50wt% in the dearsenic agent carrier at least.
Be carried on active ingredient on the carrier in the selected dearsenic agent of the present invention and be to have at least and a kind ofly be selected from IB in the periodic table of elements, IIB, VB, VIB, VIIB and VIII group 4 transition metal and/or transition metal oxide is formed.Preferred transition metal and/or transition metal oxide are to be selected from a kind of to four kinds among Mn, Fe, Ni, Pd, Pt, Au, Ag, the Zn.Preferred transition metal and/or transition metal oxide are Ag and/or Mn.The charge capacity of transition metal and/or transition metal oxide is 0.1～30wt%, and preferred charge capacity is 0.5～10wt%.
The specific surface area of dearsenic agent of the present invention is 10～500m
2/ g, pore volume are 0.1～1.5mL/g, and bulk density is 0.2～1.2g/cm
3But the machine aperture is 20～2000 .
The present invention compared with prior art has the following advantages:
1, method of the present invention is by adding hydrogen in acetylene-containing hydrocarbon, can suppress alkynes and dearsenic agent metal or/and the chemical reaction between the metal oxide, overcome the shortcoming that prior art can not be used to contain the alkine compounds dearsenification.
2, the nonactive component of dearsenic agent employing of the present invention, the active height of dearsenification under dearsenification operational condition of the present invention, the dearsenification capacity is big, and adaptability is strong, the dearsenification as acetylene-containing hydrocarbon preferably.
3, dearsenic agent preparation method of the present invention is simple, and raw material is easy to get, and the dearsenic agent preparation cost is minimized.
Embodiment
To further set forth the present invention by detailed description below, but embodiment not a limitation of the present invention to specific embodiments of the invention.
Embodiment 1:
1, the preparation of dearsenic catalyst:
In reactor, add aluminum nitrate [Al (NO
3)
39H
2O] 375.2 gram (1.0mol) and zinc nitrate [Zn (NO
3)
26H
2O] 119 gram (0.4mol) and Silver Nitrate (AgNO
3) 4.12 grams, add deionized water 200mL then, be made into the precursor solution that contains required metal component after fully stirring, in thermostatic bath, be incubated 50～55 ℃ after, drip 40wt%Na
2CO
3Solution is between the pH value of solution value 7.5～9, and the centrifugal solid materials that gets after 0.5 hour wears out.Solid materials is washed and starched with deionized water again and is washed with abundant removal soluble sodium salt, and further dry under 120 ℃, calcination was preserved standby with vacuum drier after 12 hours in 500 ℃ High Temperature Furnaces Heating Apparatus then.Specific surface area by the dearsenic agent of above-mentioned preparation method's gained is 150m
2/ g, pore volume 0.45mL/g, bulk density 0.7g/cm
3But the machine aperture is 150 .
2, the dearsenification of acetylene-containing hydrocarbon:
Get above-mentioned gained dearsenic agent 50 grams, load in the middle of internal diameter is the fixed-bed reactor of 33mm, activation cooling after 2 hours in 300 ℃ nitrogen atmosphere, feed be furnished with certain volume than hydrogen and 500ppb arsenic (with AsH
3Form exists) contain propine, propane and third rare mixed C
3Gas, temperature are controlled at 50 ℃, and pressure is 0.1MPa, and gas space velocity is 2500h
-1, hydrogen content 3% (volume), handle 200 hours continuously after, its dearsenification the results are shown in Table 1.
Embodiment 2-15:
Except that the control of conditions such as the temperature of dearsenification, pressure, gas space velocity, hydrogen content changed, all the other were operated with embodiment 1, and the quantity of temperature, pressure, gas space velocity, hydrogen content condition sees Table 1.Dearsenification the results are shown in Table 1.
Table 1
| Embodiment | Temperature (℃) | Pressure (MPa) | Hydrogen content (% volume) | Air speed (h -1) | Purify the degree of depth (ppb) | |
| Before the purification | After the purification | |||||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 | 50 100 150 50 50 50 50 0 50 50 10 30 50 50 50 | 0.1 0.1 0.1 0.05 0.5 1.0 3.0 0.1 0.01 0.1 0.1 0.1 0.1 0.1 0.1 | 3 3 3 3 3 3 3 0.1 0.5 10 40 50 3 3 3 | 2500 1000 2500 2500 2500 2500 2500 2500 2500 2500 2500 500 2000 3000 4000 | 500 100 300 500 500 800 500 1000 500 500 500 1000 500 500 500 | 5 ＜5 ＜5 30 5 7 9 230 22 ＜5 ＜5 ＜5 ＜5 15 23 |
Embodiment 16:
Get dearsenic agent 50 grams by embodiment 1 method preparation, loading in internal diameter is that 33mm gets in the middle of the fixed-bed reactor, and 300～350 ℃ down with hydrogen nitrogen mixed gas (H
2/ N
2(v/v)=1: 1) reduce after 4 hours, be cooled to 50～60 ℃.Feeding is furnished with 3.0% (volume) hydrogen and 500ppb arsenic (with AsH
3Form exists) contain propine, propane and third rare mixed C
3Gas keeps gas space velocity at 2500h
-1, handle 300 hours continuously after, detect the outlet arsenic concentration less than 5ppb.
Embodiment 17:
In reactor, add aluminum nitrate [Al (NO
3)
39H
2O] 375.2 gram (1.0mol) and zinc nitrate [Zn (NO
3)
26H
2O] 119 gram (0.4mol) and Palladous nitrate [Pd (NO
3)
23H
2O] 1.59 grams, add deionized water 200mL then, be made into the precursor solution that contains required metal component after fully stirring, in thermostatic bath, be incubated 50～55 ℃ after, drip 40wt%Na
2CO
3Solution is between the pH value of solution value 7.5～9, and the centrifugal solid materials that gets after 0.5 hour wears out.Solid materials is washed and starched with deionized water again and is washed with abundant removal soluble sodium salt, further 120 ℃ down dry, calcination is after 12 hours in 500 ℃ High Temperature Furnaces Heating Apparatus then in institute, preservation is standby in vacuum drier.The specific surface area of dearsenic agent is 250m
2/ g, pore volume 0.75mL/g, bulk density 0.65g/cm
3But the machine aperture is 90 .
By the evaluation method among the embodiment 16 dearsenic agent is carried out performance evaluation.Handle continuously after 300 hours, detect the outlet arsenic concentration less than 10ppb.
Embodiment 18:
According to embodiment 1, with 19.72 gram manganese acetate [Mn (OOCCH
3)
24H
2O] replace 4.12 to restrain Silver Nitrate (AgNO
3) make dearsenic agent.Press embodiment 1 operational condition and estimate dearsenic agent, handle 200 hours continuously after, mixed C
3The arsenic concentration of gas is reduced to less than 10ppb by 500ppb.
Embodiment 19:
Take by weighing 4.72 gram Silver Nitrate (AgNO
3) be dissolved in the 100mL deionized water, add sieve and silica-sesquioxide (Al
2O
3-SiO
2, the Si/Al ratio is 1, specific surface area 350m
2/ g, pore volume 0.55mL/g, bulk density 0.71g/cm
3But the machine aperture is 120 ) carrier 97 gram dippings 12 hours, little fire drying on electric furnace, calcination is decomposed Silver Nitrate and is got dearsenic agent in 500 ℃ High Temperature Furnaces Heating Apparatus then.Get this dearsenic agent 50 grams and estimate the dearsenification activity by embodiment 1 operational condition, handle 250 hours continuously after, mixed C
3The arsenic concentration of gas is reduced to less than 10ppb by 500ppb.
Embodiment 20:
Take by weighing 4.72 gram Silver Nitrate (AgNO
3) be dissolved in the 100mL deionized water, add aluminum oxide (Al
2O
3, specific surface area 172m
2/ g, pore volume 0.52mL/g, bulk density 0.81g/cm
3But the machine aperture is 80 ) carrier 97 gram dippings 12 hours, little fire drying on electric furnace, calcination is decomposed Silver Nitrate and is got dearsenic agent in 500 ℃ High Temperature Furnaces Heating Apparatus then.Get this dearsenic agent 50 grams and estimate the dearsenification activity by embodiment 1 operational condition, handle 250 hours continuously after, mixed C
3The arsenic concentration of gas is reduced to less than 5ppb by 500ppb.
Embodiment 21:
Get 50 grams by embodiment 19 prepared dearsenic agents, loading in internal diameter is that 33mm gets in the middle of the fixed-bed reactor, and 300～350 ℃ down with hydrogen nitrogen mixed gas (H
2/ N
2(v/v)=1: 1) reduce after 4 hours, be cooled to 50～60 ℃.Feeding is furnished with 3.0% (volume) hydrogen and 500ppb arsenic (with AsH
3Form exists) contain propine, propane and third rare mixed C
3Gas keeps gas space velocity at 2000h
-1, handle 200 hours continuously after, detect the outlet arsenic concentration less than 3ppb.
Embodiment 22:
Take by weighing 4.72 gram Silver Nitrate (AgNO
3) be dissolved in the 100mL deionized water, add silicon-dioxide (SiO
2, specific surface area 273m
2/ g, pore volume 0.82mL/g, bulk density 0.70g/cm
3But the machine aperture is 100 ) carrier 97 gram dippings 12 hours, little fire drying on electric furnace, calcination is decomposed Silver Nitrate and is got dearsenic agent in 500 ℃ High Temperature Furnaces Heating Apparatus then.Get this dearsenic agent 50 grams and estimate the dearsenification activity by embodiment 1 operational condition, handle 250 hours continuously after, mixed C
3The arsenic concentration of gas is reduced to less than 10ppb by 500ppb.
Embodiment 23:
Take by weighing 19.72 gram manganese acetate [Mn (OOCCH
3)
24H
2O] be dissolved in the 100mL deionized water, add silicon-dioxide (SiO
2) carrier 97 gram dipping 12 hours, little fire drying on electric furnace, calcination is decomposed manganese acetate and is got dearsenic agent in 300 ℃ High Temperature Furnaces Heating Apparatus then.Get this dearsenic agent 50 grams and estimate the dearsenification activity by embodiment 1 operational condition, handle 250 hours continuously after, mixed C
3The arsenic concentration of gas is reduced to less than 5ppb by 500ppb.
Embodiment 24:
Take by weighing 19.72 gram manganese acetate [Mn (OOCCH
3)
24H
2O] and 4.12 gram Silver Nitrate (AgNO
3) be dissolved in the 100mL deionized water, add silicon-dioxide (SiO
2) carrier 97 gram dipping 12 hours, little fire drying on electric furnace, calcination is decomposed manganese acetate and is got dearsenic agent in 300 ℃ High Temperature Furnaces Heating Apparatus then.Get this dearsenic agent 50 grams and estimate the dearsenification activity by embodiment 1 operational condition, handle 250 hours continuously after, mixed C
3The arsenic concentration of gas is reduced to less than 3ppb by 500ppb.
Embodiment 25:
Take by weighing 19.72 gram manganese acetate [Mn (OOCCH
3)
24H
2O] and 4.12 gram Silver Nitrate (AgNO
3) be dissolved in the 100mL deionized water, add silicon-dioxide (SiO
2) carrier 97 gram dipping 12 hours, little fire drying on electric furnace, calcination is decomposed manganese acetate and is got dearsenic agent in 300 ℃ High Temperature Furnaces Heating Apparatus then.Get this dearsenic agent 50 grams and estimate the dearsenification activity by embodiment 1 operational condition, handle 250 hours continuously after, mixed C
3The arsenic concentration of gas is reduced to less than 10ppb by 1000ppb.
Embodiment 26-31:
Take by weighing the AgNO of different mass by embodiment 1 method
3, all the other are operated with embodiment 1, the dearsenic agent that preparation has different activities component charge capacity.Get 50g respectively and carry out dearsenification performance evaluation by the operational condition of embodiment 1 from the dearsenic agent that makes, dearsenification the results are shown in following table:
Table 2
| Embodiment | Activity component load quantity (in Ag%) | Purify the degree of depth (ppb) | |
| Before the purification | After the purification | ||
| 26 27 28 29 30 31 | 0.1 0.5 5.0 10.0 25.0 30.0 | 500 500 500 500 500 500 | 200 30 ＜5 ＜5 ＜5 ＜5 |
Claims (10)
1, a kind of method that removes arsenic in the acetylene-containing hydrocarbon is characterized in that: by the fixed bed of dearsenic agent is housed, its temperature is controlled at 0～150 ℃ with acetylene-containing hydrocarbon, and pressure is 0.01～3MPa, gas space velocity≤4000h
-1Added percent by volume in the described acetylene-containing hydrocarbon and be 0.1～50% hydrogen, described dearsenic agent is by carrier and be carried on being selected from the carrier and a kind ofly among Mn, Pd, Pt, Au, Ag or the Zn form to four kinds of transition metal and/or transition metal oxide.
2, the method for claim 1 is characterized in that described temperature is controlled at 50～100 ℃, and pressure is 0.1～1MPa, gas space velocity≤2000h
-1
3, the method for claim 1 is characterized in that described acetylene-containing hydrocarbon is to contain at least a gaseous state or liquid hydrocarbon mixture in the following alkynes of 6 carbon atoms and alkane, alkene or the diolefine.
4, the method for claim 1 is characterized in that described acetylene-containing hydrocarbon is to contain gaseous state hydrocarbon mixture at least a in propine and propane, propylene or the propadiene.
5, the method for claim 1 is characterized in that the transition metal of described load and/or transition metal oxide contain Ag and/or Mn at least.
6, as claim 1 or 5 described methods, the charge capacity that it is characterized in that described transition metal and/or transition metal oxide is 0.1～30wt%.
7, as claim 1 or 5 described methods, the charge capacity that it is characterized in that described transition metal and/or transition metal oxide is 0.5～10wt%.
8, the method for claim 1, the carrier that it is characterized in that described dearsenic agent are to be selected from a kind of to three kinds in gac, aluminum oxide, magnesium oxide, zinc oxide, cupric oxide, chromic oxide, zirconium white, silicon-dioxide, titanium dioxide, sieve and silica-sesquioxide, aluminum fluoride, magnesium fluoride, chromium fluoride, ZSM-5 molecular sieve, 3A molecular sieve, 4A molecular sieve, MCM-41 molecular sieve or the USY molecular sieve.
9, the method for claim 1 is characterized in that containing at least in the described dearsenic agent carrier aluminum oxide of 50wt%.
10, the method for claim 1, the specific surface area that it is characterized in that described dearsenic agent is 10～500m
2/ g, pore volume are 0.1～1.5mL/g, and bulk density is 0.2～1.2g/cm
3, the most probable aperture is 20～2000 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137653 CN1273567C (en) | 2002-10-28 | 2002-10-28 | Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137653 CN1273567C (en) | 2002-10-28 | 2002-10-28 | Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1493661A CN1493661A (en) | 2004-05-05 |
| CN1273567C true CN1273567C (en) | 2006-09-06 |
Family
ID=34231634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02137653 Expired - Lifetime CN1273567C (en) | 2002-10-28 | 2002-10-28 | Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent |
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|---|---|
| CN (1) | CN1273567C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007147781A1 (en) * | 2006-06-21 | 2007-12-27 | Basf Se | Absorption composition and process for removing mercury |
| CN103566947B (en) * | 2012-08-07 | 2016-01-20 | 北京三聚环保新材料股份有限公司 | A kind of arsenic removal catalyst and preparation method thereof |
| CN103877931A (en) * | 2012-12-19 | 2014-06-25 | 上海工程技术大学 | Metal compound-type arsenic removal agent, preparation method and application thereof |
| FR3007415B1 (en) * | 2013-06-21 | 2016-05-27 | Ifp Energies Now | PROCESS FOR REMOVING THE ARSENIC FROM A HYDROCARBON LOAD |
| CN107413017A (en) * | 2017-09-07 | 2017-12-01 | 新泰市中医院 | A kind of apoplexia rehabilitation trainer |
| CN109589762B (en) * | 2018-12-29 | 2021-09-10 | 沈阳三聚凯特催化剂有限公司 | Gas-phase dearsenic agent and preparation method thereof |
| CN111672533B (en) * | 2020-06-28 | 2021-07-13 | 北京化工大学 | Dearsenifying catalyst and its prepn |
-
2002
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