CN101724434A - Method for purifying materials containing metal impurities - Google Patents
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- CN101724434A CN101724434A CN 200810228410 CN200810228410A CN101724434A CN 101724434 A CN101724434 A CN 101724434A CN 200810228410 CN200810228410 CN 200810228410 CN 200810228410 A CN200810228410 A CN 200810228410A CN 101724434 A CN101724434 A CN 101724434A
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Abstract
The invention relates to a method for purifying materials containing metal impurities, in particular to a method for removing at least one metal impurity of iron, sodium and calcium from hydrocarbon materials, which comprises that the materials containing metal impurities are mixed with flash gas (low grade gas) in a low-pressure separator of a hydrogenation unit to obtain the materials with a higher impurity removal rate by a fixed bed layer of filtering materials, absorbent or catalyst. Compared with the prior art, the method in the invention has mild operation conditions and high impurity removal rate, and can be used in processing various materials containing metal impurities.
Description
Technical field
What the present invention relates to a kind of containing metal impurity material takes off the heteroatoms purifying method, relate in particular to the demetalization purifying method of metallic impurity materials such as a kind of iron content, sodium or calcium, particularly remove the demetalization purifying method of metallic impurity materials such as iron in the hydrocarbon material, sodium or calcium.
Background technology
In the hydrocarbon material, as various mineral hydrocarbon materials, often contain various heteroatomss, as sulphur, nitrogen, oxygen and various metals etc.Remove the important content that various heteroatomss are hydro carbons courses of processing, many courses of processing are purpose to remove these heteroatomss all, as hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM) etc.Some other non-hydrocarbons material as all kinds of SOLVENTS and other chemical products, wherein also may contain similar metallic impurity.
Iron is a kind of common very special again class heteroatoms in hydrocarbon material and other chemical products, and on the one hand, the hydrocarbon material in various sources itself all more or less contains certain iron, and perhaps some additive of Tian Jiaing contains iron atom; On the other hand, in the course of processing, because the main raw of many equipment all comprises ferro element, therefore in the course of processing, iron atom is along with the corrosion of equipment also enters in the material.In some hydrocarbon materials, because the singularity in source wherein contains metallic impurity such as more sodium and/or calcium.
The iron contamination of hydrocarbon material can the mineral compound form exists, and form that also can organic compound exists, as mineral compound such as the oxide compound of iron, sulfide, organic compound such as iron naphthenate.Iron contamination in the hydrocarbon material can form throw out, and is highly susceptible to forming settling in some courses of processing, as in various fixed bed hydrogenation processes.Being easy to form sedimental unfavorable result is, these settlings are concentrated and are deposited in the small part beds that at first contacts with material, and then the circulation passage of stifled cold material, and quick rising falls in bed layer pressure, influences the normal running of device, even causes shut-down.So the iron contamination that removes in the hydrocarbon material is the steps necessary that guarantees downstream production equipment normal running, particularly for various hydrogenation units, it is even more important to remove iron contamination.Equally, sodium and calcium also be easy to concentrate be deposited at first with beds that material contact in, the steady running of installing is caused bigger influence.
The extraction of employing deferrization method and electromagnetic force deferrization method are arranged in the prior art.US5,078,858 to adopt oxalic acid or citric acid etc. be sequestrant, with the organic dissolved ferric iron in the liquid hydrocarbon material to aqueous phase, and further separation removal.This method is very not suitable for trace iron impurity, and inapplicable to the inorganic iron compound yet.US5,607,575, US4,836,914 grades adopt a kind of custom-designed magnet strainer, under the effect in magnetic field, remove the iron contamination in the hydrocarbon material.This method needs special equipment, and is also relatively poor to the adaptability of dissimilar iron contaminations.Take off that special-purpose demetalization material is generally adopted in sodium and decalcification or before the Primary Catalysts bed, increase the protective material bed that voidage is bigger.Adopt the adaptability of special-purpose demetalization material relatively poor, limited as decalcifying agent to taking off the sodium effect.Adopt the protective material bed to be applicable to the hydrocarbon material that metals content impurity is lower, relatively poor for the suitability of the high material of metals content impurity.
The various solid deferrization materials of main employing remove the iron contamination in the hydrocarbon material in the prior art under the condition of facing hydrogen or non-hydrogen.US3,947,347 adopt a kind of wide aperture inert particulate solid support material, and (260～454 ℃, 2MPa～20MPa) and under the hydro condition removes the iron contamination in the hydrocarbon raw material at comparatively high temps and pressure.The operational condition of this method is comparatively harsh.US4,933,071 adopts the solid, inert filamentary material, under conditions of non-hydrogen, will be in the presence of sulfide, iron is deposited on the filamentary material with the form of sulfide, and suitable dimethyl disulfide, butyl sulfhydryl, sulfur alcohol, the dimethyl sulfide sulfides of adding in the raw material, to promote the formation of iron sulfide.The deferrization rate of this patent is lower, and product is not suitable as the charging of fixed bed hydrogenation device.CN1323873A adopts the solid, inert filamentary material, operates under hydro condition, and the deferrization rate has had raising, but temperature of reaction is higher, and the deferrization effect needs further to improve.CN2465800 and CN2671682 have granule interior the napex of the catalyst-assembly of spongy structure honeycomb hole at hydrogenation catalyst layer bed, but this mode has just been alleviated the too fast problem of beds pressure drop, does not fundamentally solve the problem that bed pressure drop rises.
Summary of the invention
At the deficiencies in the prior art, the invention provides the removal methods of metallic impurity in a kind of material, the inventive method condition relaxes, and takes off the percentage of admixture height, has made full use of the resource of hydrogenation unit, and flow process is simple.
The purifying method of containing metal impurity material of the present invention specifically comprises following content:
(1) removes at least a metallic impurity in iron in the material, sodium and the calcium;
(2) flashed vapour of the light pressure separator in the material of containing metal impurity and the hydrogenation unit (the low gas that divides) mixes and contacts;
(3) after containing metal impurity material mixes with flashed vapour or in the blended while, adopting fixedly, bed of packings removes the metallic impurity in the containing metal impurity material; Fixedly bed of packings can adopt in filtering material, sorbing material and the catalyzer one or more;
(4) mixture separation is demetalization impurity material and gas phase, and demetalization impurity material and gas phase are further handled or utilized.
Wherein (1) described metallic impurity can be a kind of in iron, sodium and the calcium, also can be wherein several, simultaneously can also contain other metallic impurity, metallic impurity can be inorganic combined form or organic compound state, the total content of metallic impurity (in metallic element) is generally 1～1000 μ g/g, is generally 20～200 μ g/g.Material is hydrocarbon material or other chemical products, and hydrocarbon material generally can comprise gasoline fraction, diesel oil distillate, various vacuum distillate, heavy oil, residual oil or petroleum crude oil etc.
Hydrogenation unit described in above-mentioned (2) can be various types of hydrogenation units, as hydro-refining unit, and hydroeracking unit, hydrotreater, hydro-upgrading unit etc.The working pressure of the light pressure separator of hydrogenation unit, the pressure that is the light pressure separator flashed vapour is generally normal pressure～5MPa, usually in 0.5～3MPa scope, so hydrocarbon material mixes with flashed vapour also and can operate in being lower than this pressure range slightly, needn't be to the flashed vapour supercharging.Major part is a hydrogen in the flashed vapour of hydrogenation unit light pressure separator, importantly wherein contains more hydrogen sulfide, and the hydrogen sulfide volume content is generally 0.2%～20%, usually 2%～12%.The gas-liquid volume ratio of flashed vapour and hydrocarbon material is generally 1～1000NM
3/ NM
3, usually can be at 10～100NM
3/ NM
3Operate under the condition.Mixing temperature is envrionment temperature～300 ℃, generally operates under 50～150 ℃ of conditions.Mixing can be carried out in empty cylinder device, also can be in containing filtering material, sorbent material and catalyzer carries out in the equipment of one or more materials.Gas-liquid two-phase is concurrent flow in the same way, also can countercurrent flow.Above-mentioned light pressure separator can comprise the low-pressure gas-liquid separator and be the depriving hydrogen sulphide gas stripping column that gas is recommended matter with hydrogen that its flashed vapour or discharging gas all can be used for process of the present invention.The light pressure separator flashed vapour can also can adopt the gas of different sources to mix use separately as gaseous phase materials of the present invention.
Filtering material can be the conventional material that can filter out metal deposit in above-mentioned (3), sorbing material can be the various fixed bed beds that constitute of solid particulate that can deposition solid impurity, as silicon oxide particle, alumina particle, the fixed bed bed of one or more formations in the diatomite particle etc.Catalyzer can be the beds that load sufficient quantity hydrogenation active metals component constitutes on refractory oxide, can select in existing various heavy residual hydrogenation protective material, the heavy catalyst for hydrotreatment of residual oil etc. one or more.Filtering material, sorbing material and catalyzer can be selected a kind of, also can select several, when selecting for use when multiple, preferably comprise a kind of catalyzer at least, and the hydrocarbon material of containing metal impurity with contact with catalyzer again after other material (filtering material and/or sorbing material) contacts.When only adopting catalyzer, also can use different-grain diameter, catalyzer of different nature, different catalysts is by using in order that increase of Flow of Goods and Materials direction hydrogenation active metals content and/or bed voidage reduce.The temperature of material during by fixed bed beds such as filtering material, sorbent material or catalyzer can be envrionment temperature～300 ℃, and generally at 50～150 ℃, volume space velocity is 0.5～30h
-1, be preferably 1～10h
-1Gas-liquid mixture in above-mentioned (2) can enter filtering material, sorbent material or beds jointly, and the liquid phase after also can gas-liquid separation enters, preferably the former because hydrogen further metallic impurity in the deep removal material when existing.When being the continuous operation equipment feed, fixedly bed of packings generally can adopt two or more, when a bed of packings deposits more metallic impurity and after stopping up, carries out blocked operation.
Mixture separation is material and gas phase in above-mentioned (4), can carry out in empty cylinder device, also can directly adopt the raw material surge tank in the hydrogenation unit system.When adopting the gas-liquid counter current contact in (2), gas-liquid contanct equipment also is a gas-liquid separation equipment.Removing material behind the metallic impurity further handles on demand or utilizes.The inventive method can be used as the preprocessing process of other device raw material, also can be used as the clean system method of some products.Not only be applicable to the processing of material, also can be used for the various treating processes that contain the chemical products of similar impurity.As all kinds of SOLVENTS that can be used to be contaminated with metals and the metal subtractive process of chemical products.
The inventive method adopts the flashed vapour of hydrogenation unit mesolow separator that the material of containing metal impurity is handled, owing to contain the hydrogen sulfide of higher concentration in this flashed vapour, when this gas mix with the hydrocarbon material of containing metal impurity and and then during by filling batch such as catalyzer, the hydrogen sulfide of higher concentration can remove the metallic impurity in the hydrocarbon material (one or more in iron, calcium, the sodium) totally substantially to the obvious facilitation that removed of metallic impurity.By researching and analysing discovery, contain certain density ammonia low the branch in the gas, the existence of these ammonia has promoter action to demetalization impurity process of the present invention, possible reason is metallic impurity in the hydrocarbon material, particularly iron, sodium, calcium etc., have more amount to exist with the naphthenate form, under the promoter action of alkaline matter ammonia, these metallic impurity more are suitable for and remove.The inventive method can be under very low pressure (pressure rating identical with flashed vapour for ease of operation, can be operated under a little less than this pressure condition) and very low temperature under operate, saved facility investment expense and process cost greatly.Filling batch can remove other solid impurity in the material simultaneously, has reduced the operating load that aftertreatment device is influenced or alleviated aftertreatment device.The inventive method all has tangible removal effect to multiple metallic impurity, and especially the decreasing ratio to impurity such as iron, sodium, calcium can reach more than 99%.When particularly adopting beds, when especially adopting dissimilar catalyzer or sorbent material to be used, the decreasing ratio of impurity is higher, can reach 100%.
Description of drawings
Fig. 1 is that material of the present invention takes off a kind of typical process flow synoptic diagram of impurity.Adopt gas and liquid flowing to pass through filling batch.
Fig. 2 is that material of the present invention takes off the another kind of typical process flow synoptic diagram of impurity.Adopt gas-liquid counter current to pass through filling batch.
Embodiment
Further specify method of the present invention and effect below in conjunction with drawings and Examples.
Embodiment 1
Gasoline fraction deferrization technology.
In the processing treatment process, gasoline fraction is polluted by iron contamination, is 32 μ g/g in ferro element content, and light pressure separator flashed vapour (the low gas that divides) is a low minute gas of catalytic gasoline hydrogenation refining plant, and the hydrogen sulfide volume content is 3.4%, and pressure is 0.7MPa.Experimental program 1-1 and 1-2 adopt catalyzer, and catalyzer is the residual hydrogenation protective material FZC-102 (Raschig ring shape, diameter 5mm) of Fushun Petrochemical Research Institute's development and production.Embodiment 1-3 employing alumina particle (Raschig ring shape, outside diameter 5mm, internal diameter 2.5mm, high 6mm, aluminum oxide most probable bore dia is 15nm).The alumina particle that experimental program 1-4 is identical with scheme 1-3, and alumina particle contains potassium oxide 2wt%.Adopt the inventive method to handle, specifically press accompanying drawing 1 flow operations.Actual conditions and the results are shown in Table 1.
Table 1 gasoline fraction deferrization processing condition and result
| Experimental program | ??1-1 | ??1-2 | ??1-3 | ??1-4 |
| Temperature of reaction, ℃ | ??40 | ??90 | ??120 | ??200 |
| Reaction pressure, MPa | ??0.5 | ??0.5 | ??0.5 | ??0.5 |
| Gas/oil volume ratio | ??500 | ??300 | ??300 | ??300 |
| Volume space velocity during liquid, h -1 | ??2 | ??10 | ??10 | ??20 |
| The product iron foreign matter content, μ g/g | ??0.5 | ??0.4 | ??0.6 | ??0.5 |
Embodiment 2
Diesel oil distillate deferrization technology.
Polluted by iron contamination in the ferrous contaminants and the course of processing in the diesel oil distillate; in ferro element content is 85 μ g/g; light pressure separator flashed vapour (the low gas that divides) is a low minute gas of catalytic cracking diesel oil hydro-refining unit; the hydrogen sulfide volume content is 6.5%; pressure is 1.0MPa; catalyzer adopts residual hydrogenation protective material FZC-101 (the seven apertures in the human head ring of Fushun Petrochemical Research Institute's development and production; external diameter 16mm), FZC-102 (Raschig ring shape, diameter 5mm); volume ratio is 1: 2; the layering filling, diesel raw material at first contacts with FZC-101, contacts with FZC-102 then; adopt the inventive method to handle, specifically press accompanying drawing 1 flow operations.Comparative example with experiment method 2-1 identical operations condition, does not just adopt the low gas that divides, and the adding volume content is the gas mixture of 6.5% hydrogen sulfide in the hydrogen and adopt.Actual conditions and the results are shown in Table 2.
Table 2 diesel oil distillate deferrization processing condition and result
| Experimental program | ??2-1 | Comparative example | ??2-2 | ??2-3 | ??2-4 |
| Temperature of reaction, ℃ | ??90 | ??90 | ??110 | ??140 | ??220 |
| Reaction pressure, MPa | ??0.8 | ??0.8 | ??0.8 | ??0.8 | ??0.8 |
| Gas/oil volume ratio | ??200 | ??200 | ??200 | ??200 | ??200 |
| Experimental program | ??2-1 | Comparative example | ??2-2 | ??2-3 | ??2-4 |
| Volume space velocity during liquid, h -1 | ??2 | ??2 | ??10 | ??10 | ??20 |
| The product iron foreign matter content, μ g/g | ??0.5 | ??7.0 | ??0.4 | ??0.3 | ??0.4 |
Embodiment 3
Vacuum distillate (379～540 ℃ of boiling ranges) demetal process.
Various foreign matter contents are; iron 12 μ g/g; calcium 25 μ g/g, sodium 22 μ g/g, light pressure separator flashed vapour (the low gas that divides) is a low minute gas of vacuum distillate hydroeracking unit; the hydrogen sulfide volume content is 5.1%; pressure is 1.5MPa, and catalyzer adopts the residual hydrogenation protective material FZC-100 (seven apertures in the human head ball, external diameter 16mm) of Fushun Petrochemical Research Institute's development and production; FZC-101 (seven apertures in the human head ring; external diameter 16mm), FZC-102 (Raschig ring shape, diameter 5mm); volume ratio is 1: 2: 2; the layering filling, diesel raw material at first contacts with FZC-100, contacts with FZC-102 with FZC-101 then; adopt the inventive method to handle, specifically press accompanying drawing 2 flow operations.Actual conditions and the results are shown in Table 3.
Table 3 vacuum distillate demetal process condition and result
| Experimental program | ??3-1 | ??3-2 | ??3-3 | ??3-4 |
| Temperature of reaction, ℃ | ??55 | ??105 | ??135 | ??220 |
| Reaction pressure, MPa | ??1.2 | ??1.2 | ??1.2 | ??1.2 |
| Gas/oil volume ratio | ??100 | ??100 | ??100 | ??100 |
| Volume space velocity during liquid, h -1 | ??2 | ??10 | ??10 | ??20 |
| The product iron foreign matter content, μ g/g | ??＜0.1 | ??＜0.1 | ??＜0.1 | ??＜0.1 |
| Product calcium impurities content, μ g/g | ??0.2 | ??0.2 | ??＜0.1 | ??0.2 |
| Product sodium impurity content, μ g/g | ??0.3 | ??0.2 | ??＜0.1 | ??＜0.1 |
Embodiment 4
Vacuum distillate (259～552 ℃ of boiling ranges) demetal process.
Various foreign matter contents are; iron 10 μ g/g; calcium 27 μ g/g; sodium 23 μ g/g; light pressure separator flashed vapour (the low gas that divides) is a low minute gas of vacuum distillate hydroeracking unit; the hydrogen sulfide volume content is 10.5%; pressure is 2.5MPa, and catalyzer adopts the residual hydrogenation protective material FZC-101 (seven apertures in the human head ring, external diameter 16mm) of Fushun Petrochemical Research Institute's development and production; FZC-102 (Raschig ring shape; diameter 5mm), Hydrodemetalation catalyst FZC-201 (Herba Galii Bungei shape, diameter 1.3mm; long 5mm) volume ratio is 4: 2: 1; the layering filling, diesel raw material at first contacts with FZC-101, contacts with FZC-201 with FZC-102 then; adopt the inventive method to handle, specifically press accompanying drawing 2 flow operations.Actual conditions and the results are shown in Table 4.
Table 4 vacuum distillate demetal process condition and result
| Experimental program | ??4-1 | ??4-2 | ??4-3 | ??4-4 |
| Temperature of reaction, ℃ | ??105 | ??125 | ??145 | ??230 |
| Reaction pressure, MPa | ??1.8 | ??1.8 | ??1.8 | ??1.8 |
| Gas/oil volume ratio | ??100 | ??100 | ??100 | ??100 |
| Volume space velocity during liquid, h -1 | ??2 | ??8 | ??10 | ??20 |
| The product iron foreign matter content, μ g/g | ??＜0.1 | ??＜0.1 | ??＜0.1 | ??＜0.1 |
| Product calcium impurities content, μ g/g | ??＜0.1 | ??＜0.1 | ??＜0.1 | ??＜0.1 |
| Product sodium impurity content, μ g/g | ??＜0.1 | ??＜0.1 | ??＜0.1 | ??＜0.1 |
Embodiment 5
Crude naphthenic acid and crude phenols demetalization impurity technology.
Iron level is 35 μ g/g in the crude naphthenic acid, sodium content 420 μ g/g.Sodium content 870 μ g/g in the crude phenols, calcium contents 65 μ g/g.Light pressure separator flashed vapour (the low gas that divides) is a low minute gas of vacuum distillate hydroeracking unit; the hydrogen sulfide volume content is 5.1%; pressure is 1.5MPa; catalyzer adopts residual hydrogenation protective material FZC-100 (the seven apertures in the human head ball of Fushun Petrochemical Research Institute's development and production; external diameter 16mm); FZC-101 (seven apertures in the human head ring; external diameter 16mm), Hydrodemetalation catalyst FZC-201 (Herba Galii Bungei shape, diameter 1.3mm; long 5mm) volume ratio is 3: 2: 1; the layering filling, diesel raw material at first contacts with FZC-100, contacts with FZC-201 with FZC-101 then; adopt the inventive method to handle, specifically press accompanying drawing 1 flow operations.Actual conditions and the results are shown in Table 5.
Table 5 naphthenic acid and crude phenols demetalization impurity processing condition and result
| Experimental program | ??5-1 | ??5-2 | ??5-3 | ??5-4 |
| Raw material | Crude naphthenic acid | Crude naphthenic acid | Crude phenols | Crude phenols |
| Temperature of reaction, ℃ | ??60 | ??80 | ??60 | ??80 |
| Reaction pressure, MPa | ??1.8 | ??1.8 | ??1.8 | ??1.8 |
| Gas/oil volume ratio | ??200 | ??300 | ??200 | ??300 |
| Volume space velocity during liquid, h -1 | ??2 | ??8 | ??2 | ??8 |
| Experimental program | ??5-1 | ??5-2 | ??5-3 | ??5-4 |
| The product iron foreign matter content, μ g/g | ??0.4 | ??0.5 | ??/ | ??/ |
| Product calcium impurities content, μ g/g | ??/ | ??/ | ??0.3 | ??0.4 |
| Product sodium impurity content, μ g/g | ??0.6 | ??0.7 | ??1.2 | ??1.4 |
Claims (19)
1. the purifying method of a containing metal impurity material specifically comprises following content:
(1) removes at least a metallic impurity in iron in the material, sodium and the calcium;
(2) flashed vapour of the light pressure separator in the material of containing metal impurity and the hydrogenation unit mixes and contacts;
(3) containing metal impurity material mixes back or at blended simultaneously with flashed vapour, adopts fixedly that bed of packings removes the metallic impurity in the containing metal impurity material, fixedly in bed of packings employing filtering material, sorbing material and the catalyzer one or more;
(4) mixture separation is demetalization impurity material and gas phase, and demetalization impurity material is further handled or utilized.
2. in accordance with the method for claim 1, it is characterized in that wherein (1) described metallic impurity are a kind of in iron, sodium and the calcium, or wherein several, the total content of metallic impurity is 1～1000 μ g/g.
3. in accordance with the method for claim 2, the total content that it is characterized in that described metallic impurity is 20～200 μ g/g.
4. in accordance with the method for claim 1, it is characterized in that (1) described material is a hydrocarbon material, comprise gasoline fraction, diesel oil distillate, various vacuum distillate, heavy oil, residual oil or petroleum crude oil.
5. in accordance with the method for claim 1, it is characterized in that hydrogenation unit hydro-refining unit, hydroeracking unit, hydrotreater or the hydro-upgrading unit described in (2).
6. in accordance with the method for claim 1, the flashed vapour pressure that it is characterized in that the light pressure separator in the hydrogenation unit described in (2) is normal pressure～5MPa, and the hydrogen sulfide volume content is 0.2%～20%.
7. in accordance with the method for claim 6, the flashed vapour pressure that it is characterized in that described light pressure separator is 0.5～3MPa, and the hydrogen sulfide volume content is 2%～12%.
8. in accordance with the method for claim 1, the gas-liquid volume ratio that it is characterized in that flashed vapour described in (2) and material is 1～1000NM
3/ NM
3, mixing temperature is envrionment temperature～300 ℃.
9. in accordance with the method for claim 8, it is characterized in that described gas-liquid volume ratio is 10～100NM
3/ NM
3, mixing temperature is 50～150 ℃.
10. in accordance with the method for claim 1, it is characterized in that the sorbing material described in (3) be can deposition solid impurity the fixed bed bed that constitutes of solid particulate, described catalyzer is the beds that load sufficient quantity hydrogenation active metals component constitutes on refractory oxide.
11. in accordance with the method for claim 10, it is characterized in that described sorbing material is a silicon oxide particle, one or more in alumina particle and the diatomite particle; Attach most importance in residual hydrogenation protective material and the heavy catalyst for hydrotreatment of residual oil one or more of described catalyzer.
At least comprise a kind of catalyzer 12. it is characterized in that in accordance with the method for claim 1, the fixedly bed of packings described in (3).
13. contact with catalyzer again after contacting behind the material that it is characterized in that in accordance with the method for claim 1, containing metal impurity in (3) and filtering material and/or the sorbing material.
14. in accordance with the method for claim 12, when it is characterized in that described catalyzer is multiple, use different-grain diameter, catalyzer of different nature, different catalysts is by using in order that increase of hydrocarbon material flow direction hydrogenation active metals content and/or bed voidage reduce.
15. in accordance with the method for claim 1, the operational condition when it is characterized in that hydrocarbon material in (3) by fixing bed of packings is, temperature is envrionment temperature～300 ℃, and volume space velocity is 0.5～30h
-1
16. in accordance with the method for claim 15, the operational condition when it is characterized in that described material by fixing bed of packings is, temperature is 50～150 ℃, and volume space velocity is 1～10h
-1
17. in accordance with the method for claim 1, it is characterized in that the fixedly bed of packings during the gas-liquid mixture in (2) enters jointly (3), or the liquid phase after the gas-liquid separation enters the fixedly bed of packings in (3).
Adopt two or more blocked operations 18. it is characterized in that in accordance with the method for claim 1, the fixedly bed of packings described in (3).
19. it is characterized in that in accordance with the method for claim 1, that light pressure separator in the hydrogenation unit described in (2) comprises the low-pressure gas-liquid separator and be the depriving hydrogen sulphide gas stripping column that gas is recommended matter with hydrogen.
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| CN107201247A (en) * | 2017-05-24 | 2017-09-26 | 广昌达新材料技术服务（深圳）股份有限公司 | A kind of crude oil decalcifying device and decalcification method |
| CN107216910A (en) * | 2017-07-13 | 2017-09-29 | 深圳市广昌达石油添加剂有限公司 | A kind of crude oil load decalcifying agent, crude oil decalcifying device and its application method |
| CN111019697A (en) * | 2018-10-09 | 2020-04-17 | 中石化广州工程有限公司 | Hydrotreating method of impurity-containing raw oil |
-
2008
- 2008-10-29 CN CN 200810228410 patent/CN101724434B/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788997A (en) * | 2012-11-03 | 2014-05-14 | 中国石油化工股份有限公司 | A pretreatment method of low-sulfur high-nitrogen hydrogenation raw materials |
| CN103788997B (en) * | 2012-11-03 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of pretreatment process of low-sulfur high-nitrogen hydrogenating materials |
| CN107201247A (en) * | 2017-05-24 | 2017-09-26 | 广昌达新材料技术服务（深圳）股份有限公司 | A kind of crude oil decalcifying device and decalcification method |
| CN107201247B (en) * | 2017-05-24 | 2019-05-14 | 广昌达新材料技术服务（深圳）股份有限公司 | A kind of crude oil decalcifying device and decalcification method |
| CN107216910A (en) * | 2017-07-13 | 2017-09-29 | 深圳市广昌达石油添加剂有限公司 | A kind of crude oil load decalcifying agent, crude oil decalcifying device and its application method |
| CN111019697A (en) * | 2018-10-09 | 2020-04-17 | 中石化广州工程有限公司 | Hydrotreating method of impurity-containing raw oil |
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| CN101724434B (en) | 2012-12-26 |
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