CN1259560A - Dearsenic agent for petroleum hydrocarbon and its prepn. method and application - Google Patents
Dearsenic agent for petroleum hydrocarbon and its prepn. method and application Download PDFInfo
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- CN1259560A CN1259560A CN 98100762 CN98100762A CN1259560A CN 1259560 A CN1259560 A CN 1259560A CN 98100762 CN98100762 CN 98100762 CN 98100762 A CN98100762 A CN 98100762A CN 1259560 A CN1259560 A CN 1259560A
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Abstract
The present invention relates to petroleum hydrocarbon dearsenication agent, its prepn. method and application. Said dearsenication agent is composed of (wt.%) Ni 5-20%, Mo or W 0.5-5.0%, the rest is carrier, said carrier is one of gama Al2O3, TiO2, MgO, SiO2, Al2O3-SiO2 or their mixture; the prepn. of dearsenication agent is to dip formed carrier in dipping solution which contains Ni salt and ammonium molybdate or ammonium metatungstate and a complexing agent, then dry and roast. The invented dearsenication agent possesses high dearsenication efficiency under relatively moderate technological condition, and relatively large ability holding arsenic capacity, it can be used in the dearsenication of distillation cut oil with final boiling point lower than 400 deg.C.
Description
The technology that the present invention relates to a kind of dearsenic agent for petroleum hydrocarbon and preparation method thereof and remove the arsenic in the hydro carbons with this dearsenic agent.
Arsenide is the poisonous substance in the catalysis course of processing.The arsenide of minute quantity can make catalyzer that permanent poisoning takes place and inactivation, particularly platinum, palladium noble metal catalyst are more responsive to arsenic in the raw material.Usually arsenic content is less than 1ppb in the reforming catalyst requirement charging, and arsenide is less than 200ppb in the hydrogenation catalyst requirement charging.In order to protect cracking of ethylene subsequent technique Primary Catalysts, require in the charging of steam cracking material arsenic content less than 20ppb.Therefore, when the higher hydrocarbon raw material of processing arsenic content, must give dearsenification to raw material according to different processing requirements and handle.
The common method that removes arsenide from hydro carbons is to contain the hydrocarbon raw material of arsenide, under the certain reaction condition, a kind of solid material (dearsenic agent) of flowing through, arsenide in the raw material is adsorbed by this material and/or with this material on the reactive metal of load react and be removed.
Proposed a kind of method that removes arsenide or phosphorus from hydrocarbon polymer among the CN1030440A, wherein said dearsenic agent contains 3～50 heavy %, the nickel of best 10～50 heavy %, and wherein at least 50% nickel is the metallic reducing attitude.Its preparation method is earlier nickel salt to be deposited on SiO
2, MgO or Al
2O
3On carrier, in air,, under 250～600 ℃, reduce processing then with hydrogen in 300～600 ℃ of following roastings.The condition of dearsenification reaction is: 110～280 ℃ of temperature, pressure 1～100 crust, volume space velocity 1～5h during liquid
-1This method is used to handle heavier liquefied hydrocarbon raw material (as petroleum naphtha).
A kind of hydrocarbon dearsenicating catalyst is disclosed among the CN1095749A, be with a kind of diaspore content greater than the aluminium hydroxide of 65 heavy % and aperture greater than the aluminium hydroxide of 100nm by (0.2～5): 1 part by weight mixes and moulding, gets γ-Al through 570～670 ℃ of roastings again
2O
3Carrier immerses PH by nickel salt and ammoniacal liquor preparation with this carrier and floods in 6～11 the steeping fluid, then drying roasting and making.This catalyzer contains the Ni of 12～40 heavy %, and all the other are γ-Al
2O
3This catalyzer owing to nickel content height, need flood and roasting process for 2～3 times, and need higher temperature of reaction in the dearsenification process in preparation process.
A kind of dearsenic agent of containing arsenic oil liquefied hydrocarbon and preparation method thereof that is used to has been described among the CN1136070A.This dearsenic agent is nickeliferous active ingredient to be stated from have γ-Al that double hole channel distributes
2O
3On the carrier, Ni content is 10～50%, needs double-steeping, needs before the use with the hydrogen activation, and preparation cost is higher.
Catalyzer in the above-mentioned patent, generally adopting non-noble metal Ni is active component, nickel content is generally higher, need repeatedly dipping, Ni or NiO attached on the carrier, show as the active metallic content height with bunch stacking states, the preparation process complexity, cost is higher, and in use, the arsenic capacity is not high under the mitigation condition.
Proposed a kind of arsenic removing method that is used to handle the mineral oil of arsenic content 〉=2ppm among the USP4046674, its dearsenic agent contains the NiO of 30～70 heavy % and the MoO of 2～20 heavy %
3And a kind of inorganic oxide carrier, needing prevulcanized before using, service temperature is 232～371 ℃.This dearsenic agent metal content especially nickel content is too high, and cost is big, the operational condition harshness.
A kind of method of removing mercury and/or sulphur or arsenic from hydro carbons has been proposed among the CN1045596A.Contain at least a at least a metal N that is selected from molybdenum, tungsten and uranium of metal M that is selected from nickel, cobalt, iron, palladium and platinum in the used arsenic trapping agent, the content of metal M is 0.01～15 heavy %, and the content of metal N is 2～30 heavy %.From inventive embodiments, this trapping agent promptly is the Hydrobon catalyst of industrial common use, needs sulfuration before the use, service temperature is 180～450 ℃, and reaction conditions is harsh, and because what use is common hydrogenation catalyst, thereby its arsenic capacity is little, and the operational cycle is short.
Introduced a kind of hydrogenation catalyst and preparation method thereof among the CN1135518A, this catalyzer contains the NiO of 3～6 heavy %, the MoO of 15～25 heavy %
3P with 2～5 heavy % is used for the heavy-oil hydrogenation denitrogenation.
In common Hydrobon catalyst, active component commonly used has Ni-W, Ni-Mo, Co-Mo, Co-W etc., and Mo in the catalyzer (W) is main active component, thereby the content height, and Ni (Co) is a co-catalyst component, and content is low.But in the dearsenification process, reaction mechanism is that arsenide is mainly had an effect with active ingredient Ni and is removed, thereby common hydrogenation catalyst arsenic capacity is low, is generally 1～2wt%, and the service temperature height, and under the demulcent processing condition, dearsenification efficient is lower.
The objective of the invention is to overcome deficiency of the prior art, provide a kind of cost low, the arsenic capacity is big, dearsenification efficient height, and can under the demulcent processing condition, remove the dearsenic agent and preparation method thereof of the arsenide in the petroleum hydrocarbon and the technology that removes the arsenic in the hydro carbons with this dearsenic agent.
Hydrocarbon dearsenicating catalyst provided by the present invention is by the Ni of 5～20 heavy %, and 0.5～5.0 weighs Mo or the W of %, and a kind of carrier of surplus is formed.
It is the Ni of 10～17 heavy % that dearsenic agent provided by the present invention is preferably formed, Mo or the W of 1～3 heavy %, and a kind of carrier of surplus.
Said Ni and Mo or W can be oxidation state or sulphided state in the dearsenic agent provided by the present invention, also can be to small part be the metallic reducing attitude, and load on equably on the said carrier, wherein preferably to small part be the metallic reducing attitude.
Said carrier preferably is selected from by γ-Al in the dearsenic agent provided by the present invention
2O
3, TiO
2, MgO, SiO
2, Al
2O
3-SiO
2A kind of or two kinds mixture in them in the group of being formed, wherein γ-Al preferably
2O
3, TiO
2Or their mixture.Said γ-Al
2O
3Be to make by roasting with the aluminum oxide precursor, the present invention has no particular limits this precursor, and this precursor can be selected from unformed aluminium hydroxide, vacation-boehmite, pseudo-boehmite, gibbsite or visit in the aluminium stone one or more; Said γ-Al
2O
3Specific surface be 〉=150m
2/ g, pore volume are 〉=0.3ml/g several apertures to be 〉=3.0nm.
The shape of dearsenic agent provided by the present invention can be the special-shaped strip that generally adopts in the prior art or spherical, and the present invention has no particular limits it.
The preparation method of dearsenic agent provided by the present invention comprises:
1. a kind of oxide compound or its precursor as carrier carried out kneading and compacting according to a conventional method, after drying,, obtain a kind of carrier of moulding in 500～700 ℃ of roastings 2～6 hours;
2. 1. the immersion of the carrier of said moulding contains in the steeping fluid of a kind of Ni salt and ammonium molybdate or ammonium metawolframate and a kind of complexing agent, dipping certain hour after drying, make product contain the Ni of 5～20 heavy % and Mo or the W of 0.5～5.0 heavy %, and Ni/Mo or Ni/W atomic ratio are (10～20): 1 by butt;
3. will be 2. products therefrom 100～500 ℃ of following thermal treatments 5～24 hours.
Can also comprise among the preparation method of dearsenic agent provided by the invention 3. products therefrom is reduced processing with hydrogen before being used for hydrocarbon dearsenicating, the step that makes Ni, Mo to small part or W change into the metallic reducing attitude; Or 3. products therefrom direct dearsenification that is used for petroleum hydrocarbon with oxidation state without reduction; Or will be 3. products therefrom carry out being used further to after the prevulcanized dearsenification of petroleum hydrocarbon.
The 1. said oxide compound of step is for being selected from by γ-Al among the preparation method of dearsenic agent provided by the invention
2O
3, TiO
2, MgO, SiO
2, Al
2O
3-SiO
2A kind of or two kinds mixture in them in the group of being formed, wherein γ-Al preferably
2O
3, TiO
2Or their mixture; Said precursor is meant the material that can form said oxide compound after its roasting, for example oxyhydroxide.
Said γ-Al
2O
3Precursor be to be selected from unformed aluminium hydroxide, false boehmite, pseudo-boehmite, gibbsite or to visit in the aluminium stone one or more.
The 2. said nickel salt of step is meant their nitrate, acetate or subcarbonate among the preparation method of dearsenic agent provided by the invention, wherein is preferably nitrate or subcarbonate.
The 2. said complexing agent of step is the material that can form complex compound with reactive metal Ni, Mo, W plasma among the preparation method of dearsenic agent provided by the invention, for example ammoniacal liquor or a kind of hydroxycarboxylic acid material such as glycol acid, R-Glyceric acid, oxysuccinic acid, tartrate, gluconic acid, citric acid etc., wherein preferably ammoniacal liquor or citric acid; The consumption of said complexing agent is 0.3～5 times of total moles of used Ni salt and ammonium molybdate or ammonium metawolframate, preferred 0.5～3 times.
The 2. said dipping method of step is saturated dipping or the conventional excessive pickling process that generally adopts in the prior art among the preparation method of dearsenic agent provided by the invention.
Said among the preparation method of dearsenic agent provided by the invention to reduce the condition of handling with hydrogen be well-known to those skilled in the art, so that small part Ni and Mo or W, preferred Ni and Mo or W more than 5% changes into that to go back ortho states be precondition; The conventional condition that adopts is: 150～450 ℃ of temperature, and pressure 0.1～2.0Mpa, the recovery time is 8～48 hours, the hydrogen volume air speed is 10～1000 hours
-1(h
-1).
The technology that removes arsenide from the liquefied hydrocarbon raw material provided by the present invention comprises that be room temperature～350 ℃ with said hydrocarbon raw material in temperature, and pressure is 0.5～4.0MPa, and the raw material volume space velocity is 1～15 hour
-1, hydrogen to oil volume ratio is to contact with dearsenic agent provided by the present invention under 0～300 the condition.
Said hydrocarbon raw material is that hydrocarbon gas, gasoline, petroleum naphtha and other are done＜400 ℃ fraction oil in the technology provided by the present invention.
Preferred reaction conditions is in the technology provided by the present invention: temperature is 60～300 ℃, and pressure is 1.0～2.0MPa, and hydrogen to oil volume ratio is 5～200, and the raw material volume space velocity is 1～10 hour
-1
Dearsenic agent provided by the present invention is characterised in that and adopts Ni～Mo or Ni～W bimetal constituent element as active ingredient, Ni is a dearsenic agent master active ingredient, add auxiliary agent Mo or W simultaneously, by regulating Ni/Mo or W active metallic content, make it reach best atomic ratio, use in the preparation and contain a kind of steeping fluid of complexing agent, thus make the active ingredient of dearsenic agent of the present invention can be on carrier homodisperse and playing one's part to the full.Dearsenic agent provided by the present invention has high dearsenification efficient under than the demulcent processing condition, and bigger appearance arsenic ability is arranged, can long-term operation.Dearsenic agent of the present invention can be widely used in doing＜400 ℃ various distillates and the dearsenification of gas raw material, and purposes is wide, and adaptability to raw material is strong.
The following examples will the present invention is described further.
In each embodiment and Comparative Examples, specific surface is measured according to GB/T 5816-1995 national standard method, pore volume and can several bore dias (Yang Cuiding etc. write according to " petrochemical complex analytical procedure (RIPP test method) ", Science Press, nineteen ninety publishes) in the RIPP151-90 standard method measure.Sulphur is measured with the WK-2B Microcoulomb instrument in the oil, and nitrogen is measured with REN-1500 chemoluminescence azotometer in the oil, and arsenic is measured with RIPP 65-90 standard method (coulometry) in the oil.
Embodiment 1
The preparation of used carrier in the present embodiment explanation dearsenic agent of the present invention.
The aluminium hydroxide of getting sodium metaaluminate-sulfuric acid process preparation is (according to USP4,371, the same procedure preparation of embodiment 1 in 513) 1000g (through the sample of 120 ℃ of dryings after 12 hours), adding commercially available sesbania powder 30 grams mixes, to wherein adding the solution of forming by 40 gram citric acids, 35ml concentrated nitric acid and 700 gram water, mix according to a conventional method and pinch and extruded moulding, make the wet bar of D1.6mm trifolium-shaped, after 120 ℃ of dryings, roasting is 4 hours under 650 ℃ of conditions, make carrier a, its physical and chemical performance is listed in the table 1.
Embodiment 2
Repeat the step among the embodiment 1, different is to use the same procedure according to the embodiment among the CN85100218A 1 to replace wherein used aluminium hydroxide with the high purity aluminium hydroxide that the low-carbon alkoxy aluminium hydrolysis obtains, make carrier b, its physical and chemical performance is listed in the table 1.
Embodiment 3
Get aluminium hydroxide (with the embodiment 1) 700g and the commercially available TiO of sodium metaaluminate-sulfuric acid process preparation
2300g, and make the wet bar of D1.6mm trifolium-shaped according to the same procedure among the embodiment 1,120 ℃ of dryings, roasting is 4 hours under 650 ℃ of conditions, makes carrier c, and its physical and chemical performance is listed in the table 1.
Table 1.
Embodiment 4
Present embodiment illustrates Ni-Mo/Al provided by the invention
2O
3The preparation of dearsenic agent.
In the mixture that contains 33g basic nickel carbonate and 5g ammonium molybdate, add concentration and be 25% ammoniacal liquor 30ml and make its dissolving, add water and be made into 110ml solution, take by weighing 100g embodiment 1 gained carrier a with said solution impregnation 4 hours, filter after drying, and obtain dearsenic agent A in 450 ℃ of roastings.Its physical and chemical performance is listed in the table 2.
Embodiment 5
In the mixture that contains 33g basic nickel carbonate and 4.5g ammonium molybdate, add concentration and be 25% ammoniacal liquor 35ml and make its dissolving, add water and be made into 115ml solution, take by weighing 100g embodiment 2 gained carrier b with said solution impregnation 4 hours, filter after drying, and obtain dearsenic agent B in 450 ℃ of roastings.Its physical and chemical performance is listed in the table 2.
Embodiment 6
In the mixture that contains 22g basic nickel carbonate and 2.0g ammonium molybdate, add concentration and be 25% ammoniacal liquor 28ml and make its dissolving, add water and be made into 110ml solution, take by weighing 100g embodiment 2 gained carrier b with said solution impregnation 4 hours, filter after drying, and obtain dearsenic agent C in 450 ℃ of roastings.Its physical and chemical performance is listed in the table 2.
Embodiment 7
In the mixture that contains 40g basic nickel carbonate and 6.0g ammonium molybdate, add concentration and be 25% ammoniacal liquor 55ml and make its dissolving, add water and be made into 120ml solution, take by weighing 100g embodiment 2 gained carrier b with said solution impregnation 4 hours, filter after drying, and obtain dearsenic agent D in 450 ℃ of roastings.Its physical and chemical performance is listed in the table 2.
Embodiment 8
Present embodiment illustrates Ni-W/Al provided by the invention
2O
3The preparation of dearsenic agent.
Adding concentration in the 53g nickelous nitrate is 73.7gWO
3The ammonium metatungstate solution 6.7ml of/100ml adds citric acid 20g, and adds water and be made into 100ml solution, takes by weighing 95g embodiment 2 gained carrier b with said solution impregnation 4 hours, the filtration after drying, and obtain dearsenic agent E in 450 ℃ of roastings.Its physical and chemical performance is listed in the table 2.
Embodiment 9
In the mixture that contains 30g basic nickel carbonate and 4.5g ammonium molybdate, add concentration and be 25% ammoniacal liquor 30ml and make its dissolving, add water and be made into 90ml solution, take by weighing 100g embodiment 3 gained carrier c with said solution impregnation 4 hours, filter after drying, and obtain dearsenic agent F in 450 ℃ of roastings.Its physical and chemical performance is listed in the table 2.
Comparative Examples 1
This Comparative Examples provides a kind of dearsenic agent for preparing according to the same procedure of the embodiment among the CN1095749A 1, is designated as contrast medium-1.Its physical and chemical performance is listed in the table 2.
Comparative Examples 2
This Comparative Examples provides a kind of common hydrogenation catalyst dearsenic agent as a comparison, is designated as contrast medium-2, and it is the commerical prod that Shenyang Catalyst Plant produces, and trade names are 481-3, and it belongs to Mo-Ni type catalyzer.Be mainly used in gasoline and naphtha fraction hydrogenating desulfurization.Its physical and chemical performance is listed in the table 2.
Table 2.
Embodiment 10
Present embodiment is often to push up the dearsenification activity that oil (character sees Table 4) is estimated dearsenic agent of the present invention and contrast medium with containing the arsenic paraffinic base, and evaluation is to carry out with the small fixed hydrogenator.Before the dearsenic agent oil-feed evaluation of the present invention or reduce processings earlier, perhaps do not reduce and directly oil-feed react; When reducing when handling its condition is 350 ℃ of temperature, pressure 0.2MPa, hydrogen volume air speed 300 hours
-1Contrast medium-1 does not carry out pre-treatment and directly estimates with oxidation state.The pretreatment process of contrast medium-2 is undertaken by the method that the embodiment among the patent CN1045596A 1 provides, and promptly hydrogenation catalyst is carried out prevulcanized.During evaluation, earlier with after the pre-treatment or the dearsenic agent of not handling the pressure of normal temperature, 1.6MPa, 4.0 hours
-1The condition of stock oil volume space velocity, hydrogen/oil volume ratio of 25 under, logical oil was stablized 30 hours, changed stable reaction conditions sampling analysis product arsenic content after 10 hours then into.Table 3 has been listed the activity rating result of dearsenic agent.Ortho states is gone back in dearsenic agent one hurdle (H) expression in the table 3, (Y) expression oxidation state, (L) expression sulphided state; "-" is illustrated in this condition and estimates.
Table 3.
Table 4.
Embodiment 11
This example is a dearsenification activity of estimating dearsenic agent of the present invention with paraffinic base normal two wires oil and paraffinic base AGO, and dearsenic agent reduces processing and the same procedure evaluation of pressing embodiment 10 with hydrogen according to the same procedure of embodiment 10 before evaluation.Evaluation result is listed in table 5.Dearsenic agent of the present invention as can be seen contains arsenic raw material to various hydro carbons and has adaptability widely.
Table 5.
Embodiment 12
The appearance arsenic ability of present embodiment explanation dearsenic agent of the present invention.With the same procedure of embodiment 10 dearsenic agent B is reduced earlier, stock oil is that the listed paraffinic base of table 4 often pushes up oil and adds arsenobenzene acid again to make its arsenic content be 1000ppm, with this stock oil at 1.6MPa, 220 ℃, 6.0h
-1, H
2Carry out dearsenification under the condition of/oil (v/v)=50 and handle, the timing sampling analysis generates the arsenic content in the oil (product), calculates the appearance arsenic amount of dearsenic agent when the different arsenic-removing rate according to following formula again, and the results are shown in Table 6.
As can be seen from Table 6, dearsenic agent of the present invention has higher appearance arsenic ability.
Table 6.
| Experiment numbers | Product arsenic content ppb | Arsenic-removing rate % | Hold arsenic amount wt% |
| ????10-1 | ????＜2 | ????＞99 | ????0.047 |
| ????10-2 | ????＜2 | ????＞99 | ????0.63 |
| ????10-3 | ????209 | ????＞99 | ????1.27 |
| ????10-4 | ????849 | ????＞99 | ????4.1 |
| ????10-4 | ????1900 | ????98 | ????5.8 |
| ????10-5 | ????7000 | ????93 | ????7.4 |
| ????10-6 | ????18300 | ????82 | ????8.4 |
Claims (20)
1. a dearsenic agent for petroleum hydrocarbon is characterized in that the Ni by 5～20 heavy %, Mo or the W of 0.5～5.0 heavy %, and a kind of carrier of surplus is formed.
2. according to the dearsenic agent of claim 1, it is characterized in that it consists of the Ni of 10～17 heavy %, Mo or the W of 1～3 heavy %, and a kind of carrier of surplus.
3. according to the dearsenic agent of claim 1, wherein said Ni and Mo or W are oxidation state, sulphided state or metallic reducing attitude.
4. according to the dearsenic agent of claim 1, wherein said carrier is for being selected from by γ-Al
2O
3, TiO
2, MgO, SiO
2, Al
2O
3-SiO
2A kind of or two kinds mixture in them in the group of being formed.
5. according to the dearsenic agent of claim 4, wherein said carrier is γ-Al
2O
3, TiO
2Or their mixture.
6. according to the dearsenic agent of claim 5, wherein said γ-Al
2O
3Surface-area 〉=150m
2/ g, pore volume 〉=0.3ml/g can a few bore dia 〉=3.0nm.
7. according to the dearsenic agent of claim 1, it is shaped as special-shaped strip or spherical.
8. the preparation method of the dearsenic agent of one of claim 1～7 is characterized in that this method comprises:
1.. said oxide compound or its precursor as carrier carried out kneading and compacting according to a conventional method, after drying,, obtain a kind of carrier of moulding in 500～700 ℃ of roastings 2～6 hours;
2.. 1. the carrier of said moulding immerses and contains in the steeping fluid of a kind of Ni salt and ammonium molybdate or ammonium metawolframate and a kind of complexing agent, dipping is also dry according to a conventional method, make product contain the Ni of 5～20 heavy % and Mo or the W of 0.5～5.0 heavy %, and Ni/Mo or Ni/W atomic ratio are (10～20): 1 by butt;
3.. 2. products therefrom was 100～500 ℃ of following thermal treatments 5～24 hours.
9. according to the preparation method of claim 8, wherein step 1. in said oxide compound or its precursor as carrier be the precursor of aluminum oxide, perhaps be the precursor and the TiO of aluminum oxide
2Mixture, perhaps be the precursor and the TiO of aluminum oxide
2The mixture of precursor.
10. according to the preparation method of claim 9, wherein the precursor of said aluminum oxide is to be selected from amorphous hydroted alumina, false boehmite, pseudo-boehmite, gibbsite or to visit in the aluminium stone one or more.
11. according to the preparation method of claim 9, wherein said TiO
2Precursor be titanium hydroxide.
12. according to the preparation method of claim 8, wherein step 2. in said Ni salt be nitrate, acetate, carbonate or subcarbonate.
13. according to the preparation method of claim 12, wherein said Ni salt is nitrate or subcarbonate.
14. according to the preparation method of claim 8, wherein step 2. in said complexing agent be ammoniacal liquor or be the alcohol acid compounds that comprises glycol acid, R-Glyceric acid, oxysuccinic acid, citric acid, tartrate and gluconic acid.
15. according to the preparation method of claim 14, wherein said complexing agent is ammoniacal liquor or citric acid.
16. according to the preparation method of claim 8, wherein the consumption of said complexing agent is 0.3～5 times of total moles of used Ni salt and ammonium molybdate or ammonium metawolframate.
17. according to the preparation method of claim 16, wherein the consumption of said complexing agent is 0.5～3 times of total moles of used Ni salt and ammonium molybdate or ammonium metawolframate.
18. a technology that removes arsenide from petroleum hydrocarbon is characterized in that this technology comprises that be room temperature～350 ℃ with said hydrocarbon raw material in temperature, pressure is 0.5～4.0MPa, and the raw material volume space velocity is 1～15 hour
-1, hydrogen to oil volume ratio is to contact with the described dearsenic agent of one of claim 1～8 under 0～300 the condition.
19. according to the technology of claim 18, wherein said hydrocarbon raw material is that hydrocarbon gas, gasoline, petroleum naphtha and other are done＜400 ℃ fraction oil.
20. according to the technology of claim 18, wherein the condition of said contact is that temperature is 60～300 ℃, pressure is 1.0～2.0MPa, and hydrogen to oil volume ratio is 5～200, and the raw material volume space velocity is 1～10 hour
-1
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|---|---|---|---|
| CN 98100762 CN1115382C (en) | 1998-03-20 | 1998-03-20 | Dearsenic agent for petroleum hydrocarbon and its prepn. method and application |
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|---|---|---|---|
| CN 98100762 CN1115382C (en) | 1998-03-20 | 1998-03-20 | Dearsenic agent for petroleum hydrocarbon and its prepn. method and application |
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| CN106994351A (en) * | 2017-06-02 | 2017-08-01 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
| CN107011939A (en) * | 2017-06-02 | 2017-08-04 | 钦州学院 | A kind of method of distillate hydrogenation dearsenification |
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-
1998
- 1998-03-20 CN CN 98100762 patent/CN1115382C/en not_active Expired - Lifetime
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| CN108246302A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | Catalytic gasoline hydrodearsenization agent and preparation method and application thereof |
| CN108246242B (en) * | 2016-12-28 | 2021-05-28 | 中国石油天然气股份有限公司 | Catalytic gasoline hydrodearsenization agent and preparation method and application thereof |
| CN107011939A (en) * | 2017-06-02 | 2017-08-04 | 钦州学院 | A kind of method of distillate hydrogenation dearsenification |
| CN107011939B (en) * | 2017-06-02 | 2019-01-22 | 钦州学院 | A kind of method of distillate hydrogenation dearsenification |
| CN106994351B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
| CN106994351A (en) * | 2017-06-02 | 2017-08-01 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
| CN109251764A (en) * | 2018-09-30 | 2019-01-22 | 昆山市精细化工研究所有限公司 | A kind of Hydrodearsenic Catalyst and its preparation method and application |
| CN109251764B (en) * | 2018-09-30 | 2023-03-21 | 昆山市精细化工研究所有限公司 | Dearsenic agent and preparation method and application thereof |
| 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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