CN103316690B - Liquid hydrocarbon de-arsenic agent and preparation method thereof - Google Patents
Liquid hydrocarbon de-arsenic agent and preparation method thereof Download PDFInfo
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- CN103316690B CN103316690B CN201310279739.6A CN201310279739A CN103316690B CN 103316690 B CN103316690 B CN 103316690B CN 201310279739 A CN201310279739 A CN 201310279739A CN 103316690 B CN103316690 B CN 103316690B
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Abstract
The invention relates to a liquid hydrocarbon de-arsenic agent and a preparation method thereof. The liquid hydrocarbon de-arsenic agent is prepared by preprocessing a carrier at one time and dipping at three times and is composed of CuO serving as an active component, La2O3 and CeO2 serving as transition metals, noble metal PdO, an AgO additive and an active carbon carrier. Compared with the conventional de-arsenic agent, the de-arsenic agent provided by the invention has the advantages of being high in de-arsenic precision, relatively high in de-arsenic rate, simple in preparation process and suitable for mass production and application.
Description
[technical field]
The invention belongs to catalyst technical field.More specifically, the present invention relates to a kind of liquid hydrocarbon de-arsenic agent, also relate to the preparation method of described liquid hydrocarbon de-arsenic agent.
[background technology]
Arsenide is extensively present in liquid condition petroleum hydrocarbon, and arsenide is follow-uply processed with significantly impact to it, and a small amount of arsenide can cause catalyst poisoning.In order to avoid catalyst poisoning inactivation, the arsenide in raw material must be removed.The common method removing arsenide from hydrocarbon raw material be by arsenical raw material by solid Hydrodearsenic Catalyst, make described arsenide or adsorbed by Hydrodearsenic Catalyst, or react with the active component of Hydrodearsenic Catalyst and be removed.At present, people are for this has been some researchs, and such as US4593148 discloses a kind of method removing arsenic from air-flow, and the sorbing material that the method uses adopts coprecipitation to prepare.Domestic scientific worker has also carried out a large amount of research work, such as CN1294174A discloses a kind of light-end products Hydrodearsenic Catalyst and preparation method thereof, this catalyst adopts aluminium oxide and aluminosilicate molecular sieves to be main component, need not impregnated activated component, but it is high to produce catalyst fines cost.CN1197052A discloses a kind of method removing arsenide from liquid hydrocarbon, the Hydrodearsenic Catalyst used is the Cu oxide or copper sulfide that adopt the precipitation method to prepare, they are applicable to low-temp low-pressure and there are not hydrogen condition, but catalyst preparing is complicated, need before using through over cure, therefore preparation and running cost high.CN1278523A discloses a kind of Catalysts and its preparation method of normal temperature elimination of minute amount of arsenide in hydrocarbon, and this catalyst is by CuO, ZnO, Al
2o
3preparation method is complicated with noble metal composition, and cost is high.CN1030440A discloses a kind of method except dephosphorization and arsenide in liquid hydrocarbon, can be used for naphtha and gasoline purification, but active component nickel has hydrogenation to the unsaturated hydrocarbons in cracking gas, change material composition, need reduce more than 300 DEG C before operation, complicated operation, cost are high simultaneously.
Liquid hydrocarbon, particularly petroleum hydrocarbon complicated component, therefore require higher for Hydrodearsenic Catalyst.There is the problems such as cost is high, complicated process of preparation, arsenic capacity are low in above-mentioned Hydrodearsenic Catalyst.The present inventor by concentrating on studies, invent a kind of be applicable to Hydrodearsenic Catalyst that normal temperature removes arsenide in liquid condition petroleum hydrocarbon with and preparation method thereof.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of liquid hydrocarbon de-arsenic agent.
Another object of the present invention is to provide the preparation method of described liquid hydrocarbon de-arsenic agent.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of liquid hydrocarbon de-arsenic agent.Described liquid hydrocarbon de-arsenic agent is made up of active component CuO, transition metal and precious metal additive and absorbent charcoal carrier, composed as follows with parts by weight:
A preferred embodiment of the invention, described liquid hydrocarbon de-arsenic agent composed as follows: with parts by weight
According to another kind of preferred embodiment of the present invention, described liquid hydrocarbon de-arsenic agent composed as follows: with parts by weight
According to another kind of preferred embodiment of the present invention, the surface area of described active carbon is 300 ~ 1500m
2/ g, average pore size are 14 ~ 28nm.
According to another kind of preferred embodiment of the present invention, described La
2o
3with CeO
2mixture is La
2o
3with CeO
2weight ratio be the mixture of 1:1 ~ 4.
According to another kind of preferred embodiment of the present invention, described PdO and Ag
2o mixture is PdO and Ag
2o weight ratio is the mixture of 1:1 ~ 5.
The invention still further relates to the preparation method of described liquid hydrocarbon de-arsenic agent.
The step of the method is as follows:
Steps A: Activated Carbon Pretreatment
According in g active carbon with in the ratio of ml salpeter solution for 1:3 ~ 6, active carbon is put into 0.1 ~ 0.5mol/L salpeter solution, stirring and refluxing 1 ~ 4 hour under the condition of temperature 75 ~ 100 DEG C, then be separated, this active carbon spends deionized water to neutral, dry 10 ~ 12 hours at temperature 100 ~ 110 DEG C again, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
According in the dry pretreatment of g with in ml first time maceration extract ratio for 1:2, the Pre-Treatment of Activated charcoal of drying that steps A obtains is added in 0.038 ~ 0.365mol/L first time maceration extract lanthanum nitrate, cerous nitrate or their mixture solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours temperature 100 ~ 110 DEG C, then roasting 2 ~ 4 hours under the condition of blanket of nitrogen and temperature 250 ~ 350 DEG C;
Step C: second time dipping
According in g first time Immesion active carbon with in ml second time maceration extract ratio for 1:3, the first time Immesion active carbon that step B obtains is added in 0.26 ~ 0.95mol/L second time maceration extract copper nitrate solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours at temperature 100 ~ 110 DEG C, then roasting 2 ~ 4 hours under the condition of blanket of nitrogen and temperature 250 ~ 350 DEG C;
Step D: third time floods
According in g first time Immesion active carbon with in ml second time maceration extract ratio for 1:2, the second time Immesion active carbon that step C obtains is added in 0.005 ~ 0.015mol/L third time maceration extract palladium nitrate, silver nitrate or their mixture solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours temperature 100 ~ 150 DEG C, then roasting 2 ~ 4 hours under the condition of nitrogen atmosphere and temperature 250 ~ 350 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
A preferred embodiment of the invention, the particle size of described active carbon is φ 2.7 ~ 3.3mm, surface area is 300 ~ 1500m
2/ g, average pore size are 14 ~ 28nm.
According to another kind of preferred embodiment of the present invention, described lanthanum nitrate and cerous nitrate mixture are lanthanum nitrate and cerous nitrate weight ratio is the mixture of 1:1 ~ 4.
According to another kind of preferred embodiment of the present invention, described palladium nitrate and mixture of silver nitrate are palladium nitrate and silver nitrate weight ratio is the mixture of 1:1 ~ 5.
In more detail the present invention will be described below.
The present invention relates to a kind of liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is made up of active component CuO, transition metal and precious metal additive and absorbent charcoal carrier, composed as follows with parts by weight:
The effect of described active component CuO, transition metal promoter, precious metal additive is all energy and AsH
3form the arsenide, the elemental arsenic that generate active component and auxiliary agent Deng arsenic material generation chemical reaction, a part generates new copper, arsenic alloy, and reaches and remove AsH in raw material
3object.
The effect of described absorbent charcoal carrier is to make active component and promoter metal be supported on carrier surface, for supporting active component, makes catalyst have specific structure simultaneously, and in addition, active carbon also has certain suction-operated to the impurity of the arsenic formed.
According to the present invention, described transition metal La
2o
3with CeO
2mixture is La
2o
3with CeO
2weight ratio be the mixture of 1:1 ~ 4, the preferably mixture of 1:1.5 ~ 3.0, the more preferably mixture of 1:1.8 ~ 2.4.
According to the present invention, described precious metals pd O and Ag
2o mixture is PdO and Ag
2o weight ratio is the mixture of 1:1 ~ 5, preferably the mixture of 1:1.5 ~ 4.0, the more preferably mixture of 1:2.0 ~ 3.0.
In the present invention, the surface area of described active carbon is 300 ~ 1500m
2/ g, average pore size are 14 ~ 28nm.Preferably, the surface area of described active carbon is 400 ~ 1400m
2/ g, average pore size are 16 ~ 26nm.More preferably, the surface area of described active carbon is 500 ~ 1300m
2/ g, average pore size are 18 ~ 24nm.
Preferably, described liquid hydrocarbon de-arsenic agent composed as follows: with parts by weight
CuO, La in liquid hydrocarbon de-arsenic agent of the present invention
2o
3, CeO
2, PdO and Ag
2o content adopts the conventional instrument such as Xray fluorescence spectrometer and inductively coupled plasma atomic mass spectrometry and conventional method to measure.
The invention still further relates to the preparation method of described liquid hydrocarbon de-arsenic agent.
The step of the method is as follows:
Steps A: Activated Carbon Pretreatment
Active carbon is put into 0.1 ~ 0.5mol/L salpeter solution, stir 1 ~ 4 hour under the condition of temperature 75 ~ 100 DEG C, be then separated, this active carbon spends deionized water to neutral, dry 10 ~ 12 hours at temperature 100 ~ 110 DEG C again, obtain dry Pre-Treatment of Activated charcoal.
Active carbon is as coal, timber, shell, coconut husk, walnut shell etc. are rich in the organic material of carbon, is obtained in activation furnace under high temperature and certain pressure by pyrolysis.In this activation process, form huge surface area and pore structure gradually.
The particle size of the active carbon that the present invention uses is φ 2.7 ~ 3.3mm bar, surface area is 300 ~ 1500m2/g, average pore size is 14 ~ 28nm.Preferably, the particle size of described active carbon is φ φ 2.7 ~ 3.3mm, surface area is 400 ~ 1400m2/g, average pore size is 16 ~ 26nm.More preferably, the particle size of described active carbon is φ φ 2.7 ~ 3.3mm, surface area is 500 ~ 1300m2/g, average pore size is 18 ~ 24nm.
In the present invention, the pretreatment of described active carbon is to improve activated carbon structure, imurity-removal.
The salpeter solution concentration that Pre-Treatment of Activated charcoal uses is 0.1 ~ 0.5mol/L, preferably 0.2 ~ 0.4mol/L, more preferably 0.28 ~ 0.32mol/L
Described active carbon is 1:3 ~ 6 with the ratio of described salpeter solution.Preferably, described active carbon is 1:3 ~ 5 with the ratio of described salpeter solution.More preferably, described active carbon is 1:3 ~ 4 with the ratio of described salpeter solution.
Step B: first time floods
According in the dry Pre-Treatment of Activated charcoal of g with in ml first time maceration extract ratio for 1:2, the Pre-Treatment of Activated charcoal of drying that steps A obtains is added in 0.038 ~ 0.365mol/L first time maceration extract lanthanum nitrate, cerous nitrate or their mixture solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours temperature 100 ~ 110 DEG C; Then roasting 2 ~ 4 hours under the condition of blanket of nitrogen and temperature 250 ~ 350 DEG C; .
The first time maceration extract used in first time dipping process prepares corresponding solution according to the ratio shared by lanthana, cerium oxide or lanthana and cerium oxide mixture to take lanthanum nitrate, cerous nitrate or their mixture quality.
Described lanthanum nitrate and cerous nitrate mixture solution are the mixture solutions that lanthanum nitrate and cerous nitrate are prepared according to weight ratio 1:1 ~ 4.
The weight ratio of lanthanum nitrate and cerous nitrate is not very crucial, is not clearly to the activity influence of liquid hydrocarbon de-arsenic agent of the present invention.
Step C: second time dipping
According in g first time Immesion active carbon with in ml second time maceration extract ratio for 1:3, the first time Immesion active carbon that step B obtains is added in 0.26 ~ 0.95mol/L second time maceration extract copper nitrate solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours at temperature 100 ~ 110 DEG C, then roasting 2 ~ 4 hours under the condition of blanket of nitrogen and temperature 250 ~ 350 DEG C.
The ratio of Immesion active carbon and second time maceration extract is 1:3 for the first time, if ratio is too small be unfavorable for that homogeneous impregnation adsorbs, the excessive absorption of ratio is incomplete.
The second time maceration extract used in second time dipping process is copper nitrate solution, prepares according to catalyst proportion.
Step D: third time floods
According in g second time Immesion active carbon with in ml third time maceration extract ratio for 1:2, the second time Immesion active carbon that step C obtains is added in 0.005 ~ 0.015mol/L third time maceration extract palladium nitrate, silver nitrate or their mixture solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours temperature 100 ~ 150 DEG C.
Second time Immesion active carbon and third time maceration extract ratio be 1:2, meet incipient impregnation requirement, dipping effect is good.
Described palladium nitrate and mixture of silver nitrate are palladium nitrate and silver nitrate weight ratio is the mixture of 1:1.0 ~ 5.0.
The roasting 2 ~ 4 hours under the condition of nitrogen atmosphere and temperature 250 ~ 350 DEG C of third time Immesion active carbon, obtains described liquid hydrocarbon de-arsenic agent.
In the present invention, the pressure of described nitrogen atmosphere is 0.15 ~ 0.5MPa.
The invention still further relates to the application in the arsenide of described liquid hydrocarbon de-arsenic agent in removing petroleum liquid hydrocarbon feed.
Serviceability temperature of the present invention is low, and pressure limit is wide, and air speed is large.Concrete application conditions is:
Temperature: room temperature ~ 110 DEG C, pressure: 0.1 ~ 5MPa, volume space velocity: 0.5 ~ 4h
-1,
For liquid hydrocarbon de-arsenic agent of the present invention, in described petroleum liquid hydrocarbon feed, arsenic content should be less than 1000ppb.
Hydrodearsenic Catalyst provided by the invention has the copper with good dearsenification performance to be active component, the active carbon with good adsorption properties is adopted to be carrier, in preparation process, active carbon passes through pretreatment, remove the impurity in carrier, further increase carrier specific surface simultaneously, particularly pore size distribution is moved to macropore, optimizes pore-size distribution, enhances active component utilization rate.Make the active metal component energy of load evenly be dispersed in carrier surface, arsenic-adsorbing capacity is high, can carry out degree of depth dearsenification by liquid towards petroleum hydrocarbon at a lower temperature; Compare with existing Hydrodearsenic Catalyst, Hydrodearsenic Catalyst provided by the invention, dearsenification precision is high, and arsenic capacity is large, and preparation technology is simple.
[beneficial effect]
The invention has the beneficial effects as follows: compare with existing Hydrodearsenic Catalyst, the features such as Hydrodearsenic Catalyst of the present invention has stable performance, strong adaptability, mechanical strength is good, arsenic capacity is large, preparation technology is simple.
[detailed description of the invention]
The present invention can be understood better by following embodiment.
Embodiment 1: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 300ml concentration is 0.1mol/L salpeter solution, under the condition of temperature 75 DEG C, stirring and refluxing 1 hour, is then separated, and this active carbon spends deionized water to neutral, dry 10.0 hours at temperature 100 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The Pre-Treatment of Activated charcoal 80g of drying that steps A obtains is added in the lanthanum nitrate hexahydrate prepared by 2.66g lanthanum nitrate and 160ml deionized water, at room temperature flood 6 hours, then dry 10.5 hours temperature 100 DEG C, then roasting 2 hours under the condition of blanket of nitrogen and temperature 250 DEG C;
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 15.15g copper nitrate and 240ml deionized water, at room temperature flood 6 hours, be separated, then dry 10.8 hours at temperature 100 DEG C, then roasting 2 hours under blanket of nitrogen and temperature 250 DEG C of conditions;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added to be gone in the palladium nitrate solution of dried up preparation by 0.019g palladium nitrate and 160ml, at room temperature flood 6 hours, be separated, then dry 11.2 hours at temperature 100 DEG C, then roasting 2 hours at nitrogen atmosphere and temperature 250 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3: PdO: active carbon is 5:1:0.01:80.
Embodiment 2: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 400ml concentration is 0.25mol/L salpeter solution, under the condition of temperature 100 DEG C, stirring and refluxing 2 hours, is then separated, and this active carbon spends deionized water to neutral, dry 11.6 hours at temperature 110 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The Pre-Treatment of Activated charcoal 82g of drying that steps A obtains is added in the cerous nitrate solution prepared by 13.29g lanthanum nitrate and 164ml deionized water, at room temperature flood 12 hours, be separated, dry 12.0 hours temperature 110 DEG C, then roasting 4 hours at nitrogen atmosphere and temperature 300 DEG C;
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 24.24g copper nitrate and 246ml deionized water, at room temperature flood 12 hours, be separated, then dry 10.8 hours at temperature 110 DEG C, then roasting 4 hours under the condition of blanket of nitrogen and temperature 300 DEG C;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the palladium nitrate solution prepared by 0.188g palladium nitrate and 164ml deionized water, at room temperature flood 12 hours, be separated, then dry 11.2 hours temperature 110 DEG C, then roasting 4 hours at nitrogen atmosphere and temperature 300 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3: PdO: active carbon is 8:5:0.1:82.
Embodiment 3: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
It is 0.5mol/L salpeter solution that 100g active carbon puts into 500ml concentration, under the condition of temperature 90 DEG C, stirring and refluxing 4 hours, is then separated, and this active carbon spends deionized water to neutral, dry 12.0 hours at temperature 105 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The Pre-Treatment of Activated charcoal 84g of drying that steps A obtains is added in the lanthanum nitrate hexahydrate prepared by 26.6g lanthanum nitrate and 168ml deionized water, at room temperature flood 9 hours, be separated, then dry 10.8 hours temperature 105 DEG C, then roasting 3 hours at nitrogen atmosphere and temperature 350 DEG C;
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 30.3g copper nitrate and 252ml deionized water, at room temperature flood 9 hours, be separated, then dry 11.2 hours at temperature 105 DEG C, then roasting 3 hours at nitrogen atmosphere and temperature 350 DEG C;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the palladium nitrate solution prepared by 0.56g palladium nitrate and 168ml deionized water, at room temperature flood 9 hours, be separated, then dry 10.0 hours temperature 105 DEG C, then roasting 3 hours at nitrogen atmosphere and temperature 350 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3: PdO: active carbon is 10:10:0.3:84.
Embodiment 4: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 400ml concentration is 0.2mol/L salpeter solution, under the condition of temperature 95 DEG C, stirring and refluxing 3 hours, is then separated, and this active carbon spends deionized water to neutral, dry 10.5 hours at temperature 105 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The Pre-Treatment of Activated charcoal 86g of drying that steps A obtains is added in the cerous nitrate solution prepared by 18.95g cerous nitrate and 172ml deionized water, at room temperature flood 8 hours, be separated, then dry 10.8 hours temperature 100 DEG C, then roasting 2.5 hours at nitrogen atmosphere and temperature 300 DEG C;
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 45.45g copper nitrate and 258ml deionized water, at room temperature flood 9 hours, be separated, then dry 11.2 hours at temperature 105 DEG C, then roasting 3.5 hours at nitrogen atmosphere and temperature 350 DEG C;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the liquor argenti nitratis ophthalmicus prepared by 0.44g silver nitrate and 172ml deionized water, at room temperature flood 10 hours, be separated, then dry 11.6 hours temperature 100 DEG C, then roasting 2.5 hours at nitrogen atmosphere and temperature 350 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:CeO according to the method described in present specification
2: Ag
2o: active carbon is 15:10:0.3:86.
Embodiment 5: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 350ml concentration is 0.25mol/L salpeter solution, under the condition of temperature 100 DEG C, stirring and refluxing 3.5 hours, is then separated, and this active carbon spends deionized water to neutral, dry 10.8 hours at temperature 110 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The Pre-Treatment of Activated charcoal 88g of drying that steps A obtains is added in the cerous nitrate solution prepared by 9.47g cerous nitrate and 176ml deionized water, at room temperature flood 9 hours, be separated, then dry 11.2 hours temperature 100 DEG C, then roasting 4 hours at nitrogen atmosphere and temperature 350 DEG C
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 60.6g copper nitrate and 264ml deionized water, at room temperature flood 11 hours, be separated, then dry 11.6 hours at temperature 105 DEG C, then roasting 3.5 hours at nitrogen atmosphere and temperature 350 DEG C;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the liquor argenti nitratis ophthalmicus configured by 0.22g silver nitrate and 176ml deionized water, at room temperature flood 9 hours, be separated, then dry 12.0 hours temperature 100 DEG C, then roasting 4.0 hours at nitrogen atmosphere and temperature 350 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3: Ag
2o: active carbon is 20:5:0.15:88.
Embodiment 6: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 300ml concentration is 0.2mol/L salpeter solution, under the condition of temperature 75 DEG C, stirring and refluxing 3.5 hours, is then separated, and this active carbon spends deionized water to neutral, dry 10.8 hours at temperature 105 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The drying Pre-Treatment of Activated charcoal 90g that steps A obtains is added in the lanthanum nitrate and cerous nitrate mixture (contained lanthana and cerium oxide weight ratio 1:1) solution prepared by 2.66g lanthanum nitrate, 1.89g cerous nitrate and 180ml water, at room temperature flood 10 hours, be separated, dry 11.2 hours temperature 108 DEG C, then roasting 2.5 hours at nitrogen atmosphere and temperature 300 DEG C
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution configured by 18.18g copper nitrate and 270ml deionized water, at room temperature flood 8 hours, be separated, then dry 10.0 hours at temperature 108 DEG C, then roasting 4 hours at blanket of nitrogen and temperature 350 DEG C;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the liquor argenti nitratis ophthalmicus prepared by 0.015g silver nitrate and 180ml deionized water, at room temperature flood 8 hours, be separated, then dry 10.5 hours temperature 120 DEG C, then roasting 3 hours at nitrogen atmosphere and temperature 300 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3and CeO
2mixture (1:1): Ag
2o: active carbon is 6:2 (1:1): 0.01:90.
Embodiment 7: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 300ml concentration is 0.35mol/L salpeter solution, under the condition of temperature 95 DEG C, stirring and refluxing 3.5 hours, is then separated, and this active carbon spends deionized water to neutral, dry 11.2 hours at temperature 100 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The drying Pre-Treatment of Activated charcoal 85g that steps A obtains is added in the lanthanum nitrate and cerous nitrate mixture (contained lanthana and cerium oxide weight ratio 1:4) solution configured by 5.32g lanthanum nitrate, 15.16g cerous nitrate and 170ml deionized water, at room temperature flood 8 hours, be separated, then dry 11.6 hours temperature 104 DEG C, then roasting 2.5 hours at nitrogen atmosphere and temperature 320 DEG C;
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 36.36g copper nitrate and 255ml deionized water, at room temperature flood 9 hours, be separated, then dry 12.0 hours at temperature 100 DEG C, then roasting 3 hours at temperature 280 DEG C in nitrogen;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the palladium nitrate and mixture of silver nitrate (contained palladium oxide and silver oxide weight ratio are 1:1) solution prepared by 0.094g palladium nitrate, 0.073g silver nitrate and 170ml deionized water, at room temperature flood 10 hours, be separated, then dry 10.8 hours temperature 110 DEG C, then roasting 4 hours at nitrogen atmosphere and temperature 350 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3and CeO
2mixture (1:4): PdO and Ag
2o mixture (1:1): active carbon is 9:10:0.1 (1:1): 85.
Embodiment 8: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 300ml concentration is 0.2mol/L salpeter solution, under the condition of temperature 85 DEG C, stirring and refluxing 2 hours, is then separated, and this active carbon spends deionized water to neutral, dry 11.2 hours at temperature 106 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The drying Pre-Treatment of Activated charcoal 87g that steps A obtains is added in the lanthanum nitrate and cerous nitrate mixture (contained lanthana and cerium oxide weight ratio 1:2) solution configured by 2.66g lanthanum nitrate, 3.79g cerous nitrate and 174ml deionized water, at room temperature flood 10 hours, be separated, then dry 10.0 hours temperature 105 DEG C, then roasting 2.5 hours at nitrogen atmosphere and temperature 340 DEG C;
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 36.36g copper nitrate and 261ml deionized water, at room temperature flood 10 hours, be separated, then dry 10.5 hours at temperature 105 DEG C, then roasting 3 hours at temperature 350 DEG C in nitrogen;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the palladium nitrate and mixture of silver nitrate (contained palladium oxide and silver oxide weight ratio are 1:5) solution prepared by 0.094g palladium nitrate, 0.367g silver nitrate and 174ml deionized water, at room temperature flood 8 hours, be separated, then dry 10.8 hours temperature 100 DEG C, at nitrogen atmosphere and temperature 300 DEG C, roasting 4 hours, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3and CeO
2mixture (1:2): PdO and Ag
2o mixture (1:4): active carbon is 12:3:0.3 (1:5): 87.
Embodiment 9: the preparation of liquid hydrocarbon de-arsenic agent
The implementation step of this embodiment is as follows:
Steps A: Activated Carbon Pretreatment
100g active carbon being put into 300ml concentration is 0.2mol/L salpeter solution, under the condition of temperature 87 DEG C, stirring and refluxing 2.5 hours, is then separated, and this active carbon spends deionized water to neutral, dry 12.0 hours at temperature 104 DEG C, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
The drying Pre-Treatment of Activated charcoal 89g that steps A obtains is added in the lanthanum nitrate and cerous nitrate mixture (contained lanthana and cerium oxide weight ratio 1:3) solution configured by 3.99g lanthanum nitrate, 8.53g cerous nitrate and 178ml deionized water, at room temperature flood 10 hours, be separated, then dry 10.8 hours temperature 105 DEG C, then roasting 2.5 hours at nitrogen atmosphere and temperature 340 DEG C;
Step C: second time dipping
The first time Immesion active carbon that step B obtains is added in the copper nitrate solution prepared by 42.42g copper nitrate and 267ml deionized water, at room temperature flood 10 hours, be separated, then dry 11.6 hours at temperature 102 DEG C, then roasting 3 hours at temperature 320 DEG C in nitrogen;
Step D: third time floods
The second time Immesion active carbon that step C obtains is added in the palladium nitrate and mixture of silver nitrate (contained palladium oxide and silver oxide weight ratio are 1:2.5) solution prepared by 0.075g palladium nitrate, 0.147g silver nitrate and 178ml deionized water, at room temperature flood 8 hours, be separated, then dry 10.0 hours temperature 100 DEG C, at nitrogen atmosphere and temperature 300 DEG C, roasting 4 hours, obtains described liquid hydrocarbon de-arsenic agent.
Described liquid hydrocarbon de-arsenic agent is determined composed as follows: by weight, CuO:La according to the method described in present specification
2o
3and CeO
2mixture (1:3): PdO and Ag
2o mixture (1:2.5): active carbon is 14:6:0.14 (1:2.5): 89.
Comparative example 1 ~ 9
Comparative example 1 ~ 9 embodiment is as follows: be transformed into normally used alumina support in the art respectively by processing absorbent charcoal carrier in embodiment 1 ~ 9, so obtain the alumina support Hydrodearsenic Catalyst of comparative example 1 ~ 9.
Measure the arsenic-removing rate of Hydrodearsenic Catalyst prepared by above-described embodiment and comparative example below.
Arsenic-removing rate assay method is as follows:
Condition determination:
The oil product used is industrial naphtha, is wherein 900 ~ 1100ppb containing arsenic compounds, uses size fixed bed reactors, wherein load 10 ~ 15g Hydrodearsenic Catalyst, and at normal temperatures, liquid air speed is 10h
-1condition under running 100 hours, the arsenic content then in analysis stream fluid.
Calculate arsenic-removing rate according to the following formula:
Arsenic-removing rate=
Shen Han Liang ﹡ 100% in (the arsenic content in the arsenic content-dearsenification oil in feedstock oil)/feedstock oil.
The result of implementation of these embodiments and comparative example is listed in the table below in 1.
Table 1: the dearsenification effectiveness comparison of Hydrodearsenic Catalyst of the present invention and alumina support Hydrodearsenic Catalyst
Can clearly be seen that from upper table, compared with employing alumina support Hydrodearsenic Catalyst, the Hydrodearsenic Catalyst adopting the inventive method to prepare shows good arsenic-removing rate.
Claims (9)
1. a liquid hydrocarbon de-arsenic agent, is characterized in that it is made up of active component CuO, transition metal and precious metal additive and absorbent charcoal carrier, composed as follows with parts by weight:
The surface area of described active carbon is 300 ~ 1500m
2/ g, average pore size are 14 ~ 28nm.
2. liquid hydrocarbon de-arsenic agent according to claim 1, is characterized in that the composed as follows of it: with parts by weight
3. liquid hydrocarbon de-arsenic agent according to claim 1, is characterized in that the composed as follows of it: with parts by weight
4. the liquid hydrocarbon de-arsenic agent according to claim arbitrary in claim 1-3, is characterized in that described La
2o
3with CeO
2mixture is La
2o
3with CeO
2weight ratio be the mixture of 1:1 ~ 4.
5. the liquid hydrocarbon de-arsenic agent according to claim arbitrary in claim 1-3, is characterized in that described PdO and Ag
2o mixture is PdO and Ag
2o weight ratio is the mixture of 1:1 ~ 5.
6. the preparation method of liquid hydrocarbon de-arsenic agent according to claim arbitrary in claim 1-3, is characterized in that the step of the method is as follows:
Steps A: Activated Carbon Pretreatment
According in g active carbon with in the ratio of ml salpeter solution for 1:3 ~ 6, active carbon is put into 0.1 ~ 0.5mol/L salpeter solution, stir 1 ~ 4 hour under the condition of temperature 75 ~ 100 DEG C, then be separated, this active carbon spends deionized water to neutral, dry 10 ~ 12 hours at temperature 100 ~ 110 DEG C again, obtain dry Pre-Treatment of Activated charcoal;
Step B: first time floods
According in the dry Pre-Treatment of Activated charcoal of g with in ml first time maceration extract ratio for 1:2, the Pre-Treatment of Activated charcoal of drying that steps A obtains is added in 0.038 ~ 0.365mol/L first time maceration extract lanthanum nitrate, cerous nitrate or their mixture solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours temperature 100 ~ 110 DEG C; Then under nitrogen atmosphere with roasting under the condition of temperature 250 ~ 350 DEG C 2 ~ 4 hours;
Step C: second time dipping
According in g first time Immesion active carbon with in ml second time maceration extract ratio for 1:3, the first time Immesion active carbon that step B obtains is added in 0.26 ~ 0.95mol/L second time maceration extract copper nitrate solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours at temperature 100 ~ 110 DEG C, then roasting 2 ~ 4 hours under the condition of blanket of nitrogen and temperature 250 ~ 350 DEG C;
Step D: third time floods
According in g second time Immesion active carbon with in ml third time maceration extract ratio for 1:2, the second time Immesion active carbon that step C obtains is added in 0.005 ~ 0.015mol/L third time maceration extract palladium nitrate, silver nitrate or their mixture solution, at room temperature flood 6 ~ 12 hours, be separated, then dry 10 ~ 12 hours temperature 100 ~ 150 DEG C, then roasting 2 ~ 4 hours under the condition of nitrogen atmosphere and temperature 250 ~ 350 DEG C, obtains described liquid hydrocarbon de-arsenic agent.
7. preparation method according to claim 6, is characterized in that the particle size of described active carbon is φ 2.7 ~ 3.3mm, surface area is 300 ~ 1500m
2/ g, average pore size are 14 ~ 28nm.
8. liquid hydrocarbon de-arsenic agent according to claim 6, is characterized in that described lanthanum nitrate and cerous nitrate mixture be lanthanum nitrate and cerous nitrate weight ratio are the mixture of 1:1 ~ 4.
9. liquid hydrocarbon de-arsenic agent according to claim 6, is characterized in that described palladium nitrate and mixture of silver nitrate be palladium nitrate and silver nitrate weight ratio are the mixture of 1:1 ~ 5.
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| CN110639466B (en) | 2019-09-30 | 2020-12-01 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
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| CN1323872A (en) * | 2000-05-17 | 2001-11-28 | 中国科学院大连化学物理研究所 | Dearsenicating catalyst |
| CN100392046C (en) * | 2003-08-07 | 2008-06-04 | 上海化工研究院 | Dearsenicating agent for removing high boiling point arsonium compound in liquid-state petroleum hydrocarbon at low temperature and normal temperature |
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Effective date of registration: 20160425 Address after: 710699 No. 1 Railway Station Street, Lintong District, Shaanxi, Xi'an Patentee after: The Northwest Research Institute of Chemical Industry Address before: 710061, west two floor, Qujiang campus, Xi'an Jiao Tong University, Yanta Road, 99, Yanta District, Shaanxi, Xi'an Patentee before: Xi'an Origin Chemical Technologies Co., Ltd. Patentee before: The Northwest Research Institute of Chemical Industry |