CN1323872A - Dearsenicating catalyst - Google Patents
Dearsenicating catalyst Download PDFInfo
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- CN1323872A CN1323872A CN 00110420 CN00110420A CN1323872A CN 1323872 A CN1323872 A CN 1323872A CN 00110420 CN00110420 CN 00110420 CN 00110420 A CN00110420 A CN 00110420A CN 1323872 A CN1323872 A CN 1323872A
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Abstract
A dearsenic catalyst is characterized in that: carbon is used as catalyst carrier; the active component of catalyst include: one or several elements from Fe, Co, Ni etc elements in Eight family elements; one or several from transition metals Cr, Mo, W, Mn, Ti etc; one or several from alkli metals or alkali earth metal elements Li, Na, K, Mg, Ca etc. one or several from rare earth elements La, CE, etc.. The invented catalyst can solve the problem to remove arsenic from ethylene raw oil, it possesses high mechanical strength, possesses higher service life etc.
Description
The present invention relates to the dearsenic technique of ethene crude oil, providing a kind of especially is the dearsenic catalyst of carrier with the charcoal.
Arsenic contained in the oil has very big influence to oil deep-processing process and environmental protection, very harmful such as: arsenic to the noble metal catalyst that uses in the oil deep-processing process (Pt, Pd, etc.), (less than 10ppb) catalyzer can use several years when arsenic content is low, and (tens ppb or higher) life of catalyst has only some months even shorter when arsenic content is higher.In addition, high arsenic butter acts as a fuel also very serious to the pollution of atmospheric environment.Therefore, the higher oil product of arsenic content must carry out dearsenification to be handled, and makes arsenic content reach requirement.
US.4069140 has introduced a kind of catalyzer and using method thereof that removes arsenide from heavier hydro carbons, and this catalyzer is made up of the ferric oxide that loads on the inorganic oxide, and the dearsenification working conditions is 14Mpa, 370 ℃;
US.5082569 has introduced with coprecipitation method and has prepared NiO/Al
2O
3A kind of method of type dearsenic catalyst;
US.4046674 has introduced a kind of nickel oxide and molybdenum oxide and has loaded on dearsenic catalyst on the aluminum oxide, but finds in using that the intensity of this catalyzer is relatively poor, easy fracture, pulverizing;
γ-Al that CN.1095749 has introduced in modification
2O
3Use a kind of nickel-containing catalyst of immersion process for preparing on the carrier;
FR.2673191, FR.2673129 has introduced Al
2O
3The Ni of load, Co, Fe type dearsenic catalyst;
US.4601998 has introduced a kind of Cu-Mo-Al
2O
3The type dearsenic catalyst.
For the dearsenification of ethylene raw oil (as petroleum naphtha, solar oil etc.), above-mentioned in actual applications catalyzer also comes with some shortcomings, and the index that has does not reach the industrial application requirement, such as: the intensity of catalyzer, work-ing life, arsenic capacity etc.
The object of the present invention is to provide a kind of dearsenic catalyst efficiently, solve the dearsenification problem of ethylene raw oil, it has high physical strength, long work-ing life, bigger arsenic capacity.
The invention provides a kind of dearsenic catalyst, it is characterized in that: make support of the catalyst with charcoal, comprise the gac of carbo lignius, ature of coal charcoal and other form as the charcoal of carrier;
The activity of such catalysts component comprises:
One or more of VIII family element in the periodic table of elements such as Fe, Co, Ni, loading is 0.5-50.0%;
One or more of transition metals such as Cr, Mo, W, Mn, Ti, loading is 0.1-10.0%;
One or more of basic metal such as Li, Na, K, Mg, Ca or alkali earth metal, loading is 0.1-10.0%;
One or more of rare earth element such as La, Ce, loading are 0.1-10.0%.
These elements among the present invention are present in the catalyzer with reduced state, oxidation state or other ionic condition.
The preferable content of total active ingredient is 1.0～60.0% of total catalyst quality among the present invention, and optimum content is 5.0～40.0% of a total catalyst quality.
The present invention also provides the preparation method of above-mentioned dearsenic catalyst, it is characterized in that comprising following step:
(1) pre-treatment of charcoal carrier
Bases preimpregnation: use Na
2CO
3, K
2CO
3, NaOH, KOH, NH
3Be made into the certain density aqueous solution Deng alkaloids, charcoal is carried out immersion treatment, soaking temperature is advisable with 0-80 ℃;
Surface oxidation treatment: use H
2O
2, K
2Cr
2O
7, KMnO
4Etc. oxidisability reagent carbon surface is carried out oxide treatment, treatment temp is advisable with 0-110 ℃, and preferable temperature is 80-100 ℃;
Acid treatment: use mineral acid, as: HNO
3, HCl etc., be made into the certain density aqueous solution, the charcoal carrier is handled, the temperature of solution is controlled in the 0-120 ℃ of scope, preferable temperature range is 80-110 ℃.
(2) Preparation of catalysts
Required activeconstituents is configured to solution with the form of inorganic salt, and the one or many substep floods the charcoal carrier, and required composition is loaded on the charcoal carrier; Then, catalyzer carries out drying, and drying temperature ℃ is advisable with room temperature to 500, and drying can be carried out under protection of inert gas, as: with Ar, N
2Deng doing shielding gas.
The dearsenic catalyst of the present invention preparation adopts the charcoal carrier as solid support material, with unique pretreatment mode the charcoal carrier is handled, and the dearsenic catalyst intensity of acquisition is good, the active height of dearsenification, long service life, the dearsenification of very suitable industrial ethylene stock oil.Below by embodiment in detail the present invention is described in detail.
Embodiment 1.
(a). get coal mass active carbon 100g (activated carbon particle size 1-2mm, total pore volume 0.9ml/g, specific surface area＞600m
2/ g, granule strength 〉=160N), place the 1000ml beaker, adding 500ml concentration is the Na of 0.2 N
2CO
3The aqueous solution left standstill 24 hours under room temperature (20-30 ℃), and filtration, centrifuge dripping dried by the fire 16 hours down at 120 ℃, to dry.
(b). above-mentioned charcoal places the 1000ml beaker again, adds the 450ml deionized water, and 50ml hydrogen peroxide (30% concentration) is added a cover, and is heated to 80-85 ℃, constant temperature 2 hours, filtration, centrifuge dripping.
(c). above-mentioned charcoal places the 1000ml beaker again, adds 5NHNO
3400ml is heated to 95-100 ℃, constant temperature 3 hours, filtration, centrifuge dripping; In the 1000ml beaker, use the 500ml deionized water more at every turn, be heated to 95-100 ℃, constant temperature 30 minutes boils above-mentioned charcoal and to wash 5 times.At last, dried by the fire 16 hours down, to dry at 120 ℃.
(d). above-mentioned charcoal places the 1000ml beaker again, adds the 600ml aqueous solution, and this aqueous solution contains: 0.05MLa (NO
3)
3, 0.08MMn (AC)
2, 0.1MCa (NO
3)
2, the temperature of solution is controlled at 40-50 ℃, left standstill 8 hours, then solution is filtered.Gained charcoal carrier is inserted 80 ℃ of constant temperature 16 hours of baking oven, then 120 ℃ of constant temperature 16 hours.
(e). above-mentioned charcoal places the 400ml beaker again, adds aqueous solution 95ml, and this aqueous solution contains Ni (NO
3)
2-6H
2O80g, 65 ℃ of solution temperatures under agitation, make the charcoal carrier that solution is absorbed fully, leave standstill 24 hours, dry by the fire 16 hours in 120 ℃ of baking ovens then.In the Ar air-flow in 420 ℃ of constant temperature 6 hours.Get catalyzer 126g.
(f). get above-mentioned catalyzer 50g, the internal diameter of packing into is under 300 ℃ of stainless steel reactor of 25mm, with containing H
218% N
2, H
2Gas mixture reduction 8 hours is then at H
2Dividing potential drop is 2.2Mpa, 180 ℃ of temperature of reaction, liquid air speed 8h
-1Under the condition, feeding arsenic content is the petroleum naphtha of 2680ppb.At reactor outlet, the arsenic content that detects petroleum naphtha is 3-6ppb.
Adopt the method for following accelerator activator inactivation, indexs such as effective arsenic capacity of catalyzer, physical strength are estimated: at H
2Dividing potential drop is 2.2Mpa, and temperature is 300 ℃, and the liquid air speed is 8h
-1Condition under, be that the high arsenic raw material of 60PPm oil is by beds for some time (such as 10-16 hour), again at H with the arsenic content of configuration
2Dividing potential drop is 2.2Mpa, 180 ℃ of temperature of reaction, liquid air speed 8h
-1Under the condition, feeding arsenic content is the petroleum naphtha of 2680ppb, the arsenic content of detection reaction device outlet petroleum naphtha.Repeat when the arsenic content of reactor outlet petroleum naphtha reaches 30-40ppb, catalyzer to be drawn off from reactor in the said process, particle is intact, still keeps original physical strength; The arsenic content that detects catalyzer has reached 9.1% of own quality, expects that this catalyzer has long work-ing life.
Embodiment 2:
In the foregoing description 1, replace the ature of coal charcoal with the almond charcoal, other raw material of catalyzer and preparation, evaluation method are all with embodiment 1.The particle diameter of this almond charcoal is 1-2mm, total pore volume 0.8ml/g, specific surface area 800m
2/ g, granule strength＞180N.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 3-6ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 8.2% of own quality.
Embodiment 3:
In the foregoing description 1, replace the ature of coal charcoal with the coconut husk charcoal, the particle diameter of this coconut husk charcoal is 1-2mm, total pore volume 0.9ml/g, specific surface area 850m
2/ g, granule strength＞180N prepares identical with embodiment 1 with the reaction evaluating condition.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 3-6ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 8.6% of own quality.
Embodiment 4
In the foregoing description 1, replace the ature of coal charcoal with certain model carbo lignius, the granularity of this carbo lignius is 2-4mm, total pore volume 0.8ml/g, specific surface area 780m
2/ g, granule strength＞170N prepares identical with embodiment 1 with the reaction evaluating condition.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 3-6ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 11.3% of own quality.
Embodiment 5
In (a) process of the foregoing description 1, replace 0.2N Na with 0.25NKOH
2CO
3, other preparation is fully identical with embodiment 1 with reaction evaluating.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 3-6ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 7.8% of own quality.
Embodiment 6
In (b) process of the foregoing description 1, be the KMnO of 4.0M with 40ml concentration
4Replace 50ml hydrogen peroxide (30% concentration), other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 1-3ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 7.7% of own quality.
Embodiment 7
In (d) process of the foregoing description 1, with 0.05M Na
2Cr
2O
7, 0.08MCe (NO
3)
3, replace used La
3+, Mn
2+, Ca
2+Deng solution, other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 5-8ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 9.2% of own quality.
Embodiment 8
In (e) process of the foregoing description 1, with 15gFe (NO
3)
3-6H
2O, 15gCo (NO
3)
2-6H
2O and 75gNi (NO
3)
2-6H
2O replaces former in 80gNi (NO
3)
2-6H
2O, other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 1-2ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 8.5% of own quality.
Embodiment 9
In the foregoing description 1, with 2.8gCa (NO
3)
2And 150gNi (NO
3)
2-6H
2O replaces former in 80gNi (NO
3)
2-6H
2O, other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 1-2ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 11.9% of own quality.
Embodiment 10
In the foregoing description 1, with 1.5gLa (NO
3)
3, 3.3gMnCl
2And 78gNi (NO
3)
2-6H
2O replaces former in 80gNi (NO
3)
2-6H
2O, other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 1-2ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 9.8% of own quality.
Embodiment 11
In the foregoing description 1, with 3.0gBa (NO
3)
2, 10.5gKMo
2O
7And 90gNi (NO
3)
2-6H
2O replaces former in 80gNi (NO
3)
2-6H
2O, other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 1-2ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 10.8% of own quality.
Embodiment 12
In (e) process of the foregoing description 1, omit " in the Ar air-flow, drying by the fire 6 hours " step in 420 ℃.Other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 8-10ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 8.4% of own quality.
Embodiment 13
In (a) process of the foregoing description 1, " under room temperature (20-30 ℃), left standstill 24 hours " to boil replacement in 3 hours.Other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 6-8ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 6.9% of own quality.
Embodiment 14
In the process of the foregoing description 1 (d),, change " boiling 3 hours " into " under 40-50 ℃, leaving standstill 8 hours "; Other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 10-15ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 6.2% of own quality.
Embodiment 15
(e) changes room temperature into " 65 ℃ of fluid temperatures " in the process of the foregoing description 1, and other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 5-8ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 8.7% of own quality.
Embodiment 16
In the process of the foregoing description 1 (e), " under agitation, the charcoal carrier absorbs solution fully " changed into " under the state of vacuumizing (vacuum tightness 8-10mmHg), the charcoal carrier absorbs solution fully ".
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 2-4ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 9.5% of own quality.
Embodiment 17
In the foregoing description 1, (e) in the process repeated secondary again, back secondary Ni (NO
3)
2-6H
2The consumption of O is respectively 60g and 55g.Other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.Get catalyzer 158g.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 2-4ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 15.8% of own quality.
Embodiment 18
In (f) process of the foregoing description 1, change petroleum naphtha into solar oil (arsenic content 880ppb), other preparation is identical with embodiment 1 with the reaction evaluating conditionally complete.The arsenic content that detects solar oil at reactor outlet is 2-4ppb.
Comparative example 1
In the foregoing description 1, in the omission process (a) and (b), other is constant.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 8-10ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 2.9% of own quality.
Comparative example 2
In the foregoing description 1, in the omission process (d), other is constant again.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 5-8ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 1.8% of own quality.
Comparative example 3
In the foregoing description 1, in the omission process (d), other is constant again.
The reaction evaluating result is: reactor inlet petroleum naphtha arsenic content is 2680ppb, exports to be 3-6ppb.High arsenic with preparation contains gauging (60PPm), makes catalyzer quicken inactivation, and when the reactor outlet arsenic content reached 30-40ppb, the arsenic capacity of catalyzer had reached 3.9% of own quality.
Claims (7)
1, a kind of dearsenic catalyst is characterized in that:
Make support of the catalyst with charcoal, comprise the gac of carbo lignius, ature of coal charcoal and other form as the charcoal of carrier;
The activity of such catalysts component comprises:
One or more of VIII family element in the periodic table of elements such as Fe, Co, Ni, loading is 0.5-50.0%;
One or more of transition metals such as Cr, Mo, W, Mn, Ti, loading is 0.1-10.0%;
One or more of basic metal such as Li, Na, K, Mg, Ca or alkali earth metal, loading is 0.1-10.0%;
One or more of rare earth element such as La, Ce, loading are 0.1-10.0%.
2, by the described dearsenic catalyst of claim 1, it is characterized in that: total active component content is 1.0～60.0% of a total catalyst quality.
3, by the described dearsenic catalyst of claim 2, it is characterized in that: total active component content is 5.0～40.0% of a total catalyst quality.
4, the preparation method of the described dearsenic catalyst of a kind of claim 1 is characterized in that comprising following step:
(1) pre-treatment of charcoal carrier
Bases preimpregnation: use Na
2CO
3, K
2CO
3, NaOH, KOH, NH
3Alkaloids is made into the aqueous solution, and charcoal is carried out immersion treatment, soaking temperature 0-80 ℃;
Surface oxidation treatment: use H
2O
2, K
2Cr
2O
7, KMnO
4Oxidisability reagent carries out oxide treatment to carbon surface, treatment temp 0-110 ℃;
Acid treatment: use inorganic acid aqueous solution, the charcoal carrier is handled, the temperature of solution is controlled in the 0-120 ℃ of scope;
(2) Preparation of catalysts
Required activeconstituents is configured to solution with the form of inorganic salt, and the one or many substep floods the charcoal carrier, and required composition is loaded on the charcoal carrier; Then, catalyzer carries out drying, and drying temperature ℃ is a surname with room temperature to 500.
5, by the preparation method of the described dearsenic catalyst of claim 4, it is characterized in that: the surface oxidation treatment temperature of charcoal carrier is 80-100 ℃.
6, by the preparation method of the described dearsenic catalyst of claim 4, it is characterized in that: HNO is adopted in the acid treatment of charcoal carrier
3, HCl, temperature range is 80-110 ℃.
7, by the preparation method of the described dearsenic catalyst of claim 3, it is characterized in that: the drying of catalyzer is carried out under protection of inert gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110420 CN1323872A (en) | 2000-05-17 | 2000-05-17 | Dearsenicating catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00110420 CN1323872A (en) | 2000-05-17 | 2000-05-17 | Dearsenicating catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1323872A true CN1323872A (en) | 2001-11-28 |
Family
ID=4580411
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00110420 Pending CN1323872A (en) | 2000-05-17 | 2000-05-17 | Dearsenicating catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1323872A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386141C (en) * | 2005-07-20 | 2008-05-07 | 上海自来水市北科技有限公司 | Composite absorption material for removing arsenic from water and its prepn. method |
| CN102059093B (en) * | 2009-11-18 | 2012-10-10 | 中国科学院生态环境研究中心 | Arsenic and fluorine removing nano-composite adsorbent |
| CN103316690A (en) * | 2013-07-04 | 2013-09-25 | 西安元创化工科技股份有限公司 | Liquid hydrocarbon de-arsenic agent 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 |
| CN104474662A (en) * | 2014-11-18 | 2015-04-01 | 昆明理工大学 | Preparation method of stabilizer for treating arsenic-containing waste residue |
| CN113231067A (en) * | 2021-05-28 | 2021-08-10 | 中国海洋石油集团有限公司 | Dearsenic agent for hydrogenation of light distillate oil and preparation method and application thereof |
-
2000
- 2000-05-17 CN CN 00110420 patent/CN1323872A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386141C (en) * | 2005-07-20 | 2008-05-07 | 上海自来水市北科技有限公司 | Composite absorption material for removing arsenic from water and its prepn. method |
| CN102059093B (en) * | 2009-11-18 | 2012-10-10 | 中国科学院生态环境研究中心 | Arsenic and fluorine removing nano-composite adsorbent |
| 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 |
| CN103316690A (en) * | 2013-07-04 | 2013-09-25 | 西安元创化工科技股份有限公司 | Liquid hydrocarbon de-arsenic agent and preparation method thereof |
| CN104474662A (en) * | 2014-11-18 | 2015-04-01 | 昆明理工大学 | Preparation method of stabilizer for treating arsenic-containing waste residue |
| CN104474662B (en) * | 2014-11-18 | 2017-05-10 | 昆明理工大学 | Preparation method of stabilizer for treating arsenic-containing waste residue |
| CN113231067A (en) * | 2021-05-28 | 2021-08-10 | 中国海洋石油集团有限公司 | Dearsenic agent for hydrogenation of light distillate oil and preparation method and application thereof |
| CN113231067B (en) * | 2021-05-28 | 2023-08-22 | 中国海洋石油集团有限公司 | Dearsenifying agent for light distillate oil hydrogenation and preparation method and application thereof |
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