CN1896188A - Stabilized hydrogenation of coal liquefied oil - Google Patents
Stabilized hydrogenation of coal liquefied oil Download PDFInfo
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- CN1896188A CN1896188A CN 200510083898 CN200510083898A CN1896188A CN 1896188 A CN1896188 A CN 1896188A CN 200510083898 CN200510083898 CN 200510083898 CN 200510083898 A CN200510083898 A CN 200510083898A CN 1896188 A CN1896188 A CN 1896188A
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- hydrogen
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- hydrogenation
- liquefied coal
- coal coil
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Abstract
A hydrogenation stabilizing method of coal liquefied oil is carried out by filtering coal liquefied oil, entering it and hydrogen into expanded bed reactor from reactor bottom, contacting with hydrogenation refined catalyst, gas-liquid separating, distilling, separating, circulating for hydrogen-enriched flow separated and returning it to expanded bed reactor. It has slower reactor pressure raising speed, longer working period, better catalyst activity and coal liquefied oil quality.
Description
Technical field
The present invention relates to the method that a kind of liquid hydrocarbon that coal destruction hydrogenation is obtained carries out hydrotreatment.More particularly, be a kind of hydrofinishing process of liquefied coal coil.
Background technology
Just having begun DCL/Direct coal liquefaction produced the liquid hydrocarbon product Study on Technology as far back as 1913 in Germany, and will make the skilled industryization of gasoline with the brown coal direct liquefaction in nineteen twenty-seven.Since the world oil crisis first time taking place in 1973, direct coal liquefaction technology is subjected to the attention of developed country, has developed many DCL/Direct coal liquefaction technologies in succession.
Owing to contain a large amount of alkene in the liquefied coal coil, nitrogen content is generally more than 0.5%, also contain a certain amount of oxygen,, very easily generate and be unfavorable for subsequent transportation and substances processed if untimelyly carry out pre-treatment, therefore to adopt the method for hydrogenation that liquefied coal coil is carried out pre-treatment, alkene in the saturated liquefied coal coil removes oxygen, removes heteroatomss such as nitrogen and sulphur to greatest extent, improve the stability of liquefied coal coil, so claim that also this hydrogenation process is stabilized hydrogenation.Because liquefied coal coil was as hydrogen supply agent after most of coal liquefaction crafts needed a certain amount of hydrogenation, the technology that has will be as the independent hydrogenation of the liquefied coal coil of hydrogen supply agent, and all the other liquefied coal coils go out coal liquification device as product, the technology that has is with the whole hydrofinings of liquefied coal coil, improve stability, produce hydrogen supply agent simultaneously.
US6190542 discloses a kind of technology of online hydrofining liquefied coal coil, the charging of online hydrogenation unit is petroleum naphtha and diesel oil distillate or the full cut of liquefied coal coil, by the heteroatoms in the online hydrogenation and removing liquefied coal coil, improve liquefied coal coil stability, be gelatin liquefaction part producing hydrogen supply agent simultaneously.So-called online hydrogenation technique is meant that the coal liquification device of hydrogenation unit and upstream is serially connected, and shared hydrogen source, hydrogenation unit is shutting down voluntarily, and the hydrogenation unit shutting down influences other device running, and the hydrogenation unit running also can be subjected to the influence of other device running status.
US5332489 discloses a kind of method with hydrocracking process reconstructed coal liquefaction oil, and this method is with the hydrogen supply agent of partial hydrogenation crackate as the gelatin liquefaction part, and all the other products go out coal liquification device as the product of coal liquification device.
Above-mentioned prior art all adopts conventional fixed-bed reactor, and unconverted coal dust and catalyst for coal liquefaction can be deposited on the top of reactor, cause the very fast rising of reactor pressure decrease, shortens on-stream time; Metal that contains in the liquefied coal coil and bituminous matter etc. can be deposited on reactor top catalyst surface, cause reactor top catalyzer rapid deactivation.
Summary of the invention
The objective of the invention is on the prior art basis, to provide a kind of method of liquefied coal coil stabilized hydrogenation, to prolong on-stream time.
Method provided by the invention comprises: liquefied coal coil enters expanded bed reactor with hydrogen from reactor bottom after filtering, contacts with Hydrobon catalyst, and reactor effluent separates obtaining product through gas-liquid separation, fractionation; Loop back expanded bed reactor from the isolated hydrogen rich stream of high-pressure separator.
Method provided by the invention adopts expanded bed reactor, alleviates the too fast phenomenon of reactor pressure decrease rising effectively, and the too fast inactivation of inhibited reaction device catalyst at inlet, prolongs on-stream time, can remove nitrogen in the liquefied coal coil simultaneously, improves the liquefied coal coil quality.
Description of drawings
Accompanying drawing is the method flow synoptic diagram of liquefied coal coil stabilized hydrogenation provided by the present invention.
Embodiment
The present invention adopts the method for off-line that liquefied coal coil is carried out stabilized hydrogenation, adopts the off-line hydrogenation can avoid being rich in the liquefied coal coil influence of water vapour to Hydrobon catalyst, CO in the upstream gelatin liquefaction part gas phase
xCan not enter the stabilized hydrogenation device, reduce by CO
xHydrogenation generates CH
4The meaningless hydrogen consumption that causes.The off-line hydrogenation technique can be avoided the influence of gelatin liquefaction part unplanned shutdown to the stabilized hydrogenation device.As adopt online hydrogenation technique, and if gelatin liquefaction partly goes wrong, cause hydrogenation unit to stop in emergency, when temperature of reactor drops to below 100 ℃, the water in the gas phase can be absorbed by catalyzer, causes the catalyzer mechanical property to descend, and has a strong impact on catalyst life.
One of characteristics of the present invention are to adopt expanded bed reactor.Expanded bed reactor with the fixed-bed reactor difference structurally of routine is:
1. expanded bed reactor is following charging top discharge, charging distribution mouth is positioned at reactor bottom, differing of its structure and fixed-bed reactor is bigger, the general vesicular structure that adopts is realized the charging uniformly distributing, and fixed-bed reactor are last charging bottom discharge, charging distribution mouth is positioned at reactor head, generally adopts blister configuration to carry out charging and distributes, and needs set out material collection mouth at reactor bottom.
2. expanded bed reactor catalyst bed layer height can change with inlet amount and character, and the granules of catalyst that is positioned at the beds top may upwards float with raw material, so establish the interception net at the top of beds.
Liquefied coal coil and hydrogen mix the back and enter reactor from reactor bottom, and the catalyzer in the stirring bed upwards floats, unconverted coal dust in the liquefied coal coil and catalyst for coal liquefaction can not be deposited on the reactor inlet place like this, but are evenly distributed in the reactor.Simultaneously, because the expanded bed reactor catalyzer is not in fluidized state.Reaction is produced in the thing can not contain unconverted coal dust and part catalyst for coal liquefaction, helps the further processing treatment of downstream unit to the stabilized hydrogenation liquefied coal coil.At this moment because beds is in swelling state, granules of catalyst can be in reactor bed sluggish flow, metal and bituminous matter can be deposited on the reactor bed catalyst surface more equably in the liquefied coal coil like this, help prolong operation cycle.
Because the stabilized hydrogenation device mainly is to produce hydrogen supply agent for the gelatin liquefaction unit in DCL/Direct coal liquefaction technology, the main purpose of stabilized hydrogenation is the alkene in the saturated liquefied coal coil and will be as far as possible be mononuclear aromatics with polycyclic aromatic hydrocarbons is saturated, as far as possible not with mononuclear aromatics saturated be naphthenic hydrocarbon, as seen the operating severity of stabilized hydrogenation device can not be too high, so consider the stabilized hydrogenation device one or more bed expansion bed bioreactors only are set, and other reactor is not set thereafter.
Another characteristics of the present invention are to adopt the high Hydrobon catalyst of hydrodenitrogenationactivity activity, this is because the liquefied coal coil nitrogen content is very high, sulphur content is relatively low, the stabilized hydrogenation device is if denitrogenation to greatest extent, the nitrogen content of hydrogen supply agent is low, thereby reduce the nitrogen content of liquefied coal coil on the whole, and improved the quality of liquefied coal coil, help the further processing treatment of downstream unit.
The present invention also has distinguishing feature on flow arrangement, not good enough for preventing gelatin liquefaction part tripping device separating effect, cause liquefied coal coil too much to carry gelatin liquefaction process catalyst system therefor and unconverted coal dust secretly, before stabilized hydrogenation device feedstock pump, install filtration unit additional, filter out the solid particulate in the liquefied coal coil, prevent the too fast inactivation of Hydrobon catalyst, improve the Hydrobon catalyst life-span.
Operational path of the present invention can be summarized as follows:
The present invention adopts the off-line hydrogenation technique to carry out the liquefied coal coil stabilized hydrogenation, liquefied coal coil after filtration, filter and mix with hydrogen-rich gas after carrying catalyzer and unconverted coal dust in the liquefied coal coil, enter process furnace again with after the heat exchange of stabilized hydrogenation product, enter expanded bed reactor from reactor bottom then, the stabilized hydrogenation reactor effluent mainly is included in the NH that removes in the hydrofining reactor
3, H
2S, H
2Treated oil after O and the hydrotreatment, reaction product loops back reactor through the fractionation of the hot high score flow process of routine for the high pressure hydrogen-rich gas, and coal mine gas enters the gas pipe network, and the liquid product fractionation is naphtha fraction, coal diesel oil distillate and tail oil cut.In addition owing to NH in the hydrofining reactor effluent
3Content higher, strengthen the water injection rate before the air cooling, to remove the NH in the hydrofining reactor effluent
3
The used Hydrobon catalyst of the present invention is VIA or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, and the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni has very high hydrodenitrogenationactivity activity.
The raw materials used liquefied coal coil of method of the present invention is the product liquid that coal obtains through direct liquefaction, and its boiling range is C
5～520 ℃ are preferably C
5～450 ℃.If the liquefied coal coil cut is heavy more, then the content of impurity such as its metal and bituminous matter is high more, and is big more to the influence in Hydrobon catalyst life-span.Nitrogen content is not more than 2.0 heavy % in the raw material, preferably is not more than 1.2 heavy %; Sulphur content is not more than 5.0 heavy %.The raw material oil properties is largely depended in technological operation handiness of the present invention, as nitrogen content, aromaticity content, boiling range scope etc.
Reaction conditions of the present invention is: hydrogen dividing potential drop 4.0～30.0MPa, 280～450 ℃ of temperature of reaction, liquid hourly space velocity 0.1～10h
-1, hydrogen-oil ratio 300～2800v/v.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is the method flow synoptic diagram of liquefied coal coil stabilized hydrogenation provided by the present invention.Omitted some utility appliance such as pump, air cooler and valve etc. among the figure, but this is known to those of ordinary skills.
The method flow of liquefied coal coil stabilized hydrogenation provided by the present invention is as follows:
Liquefied coal coil is after pipeline 2 enters filtration unit 3 filtrations, remove the part solid particulate of carrying secretly in the liquefied coal coil, boost to reaction pressure by feedstock pump, mix with hydrogen-rich gas, by interchanger 5 heat exchange, again after process furnace 6 heating from pipeline 4, enter stabilized hydrogenation expanded bed reactor 8 from the bottom through pipeline 7, by contacting, remove impurity, saturation of olefins and polycyclic aromatic hydrocarbonss such as metal in the stock oil, sulphur and nitrogen with beds.Because hydrofining is strong exothermal reaction,, need to introduce cold hydrogen, control reaction temperature at the reactor beds interlayer if reactor is provided with a plurality of beds.The effluent of stabilized hydrogenation reactor 8 is after pipeline 9 enters interchanger 5 heat exchange, enter high pressure hot separator 11 through pipeline 10, in high pressure hot separator, be separated into two bursts of logistics, wherein one is hot hydrogen-rich stream, wherein be mainly hydrogen and part hydrocarbon gas, also comprise partial vulcanization hydrogen and ammonia, this hot hydrogen-rich stream enters cold high pressure separator 13 and is divided into two bursts of logistics, one is a hydrogen-rich gas, wherein be mainly hydrogen, also comprise partial vulcanization hydrogen and ammonia, through recycle compressor compression after pipeline 14 with after new hydrogen from pipeline 1 mixes, loops back reactor 8 through pipeline 4; Another burst logistics of high pressure hot separator 11 then enters thermal low-pressure separators 16 through pipeline 12, further removes lighter hydrocarbons and dissolved hydrogen; The top effluent of thermal low-pressure separators 16 enters cold low separator 19 after mixing through pipeline 17 with from the cold high pressure separator 13 bottom effluents of pipeline 15, is separated into coal mine gas and liquid hydrocarbon, coal mine gas as product through pipeline 20 dischargers; The bottom effluent of cold low separator 19 is after pipeline 21 and the thermal low-pressure separators 16 bottom effluents mixing from pipeline 18, enter separation column 23 through pipeline 22, fractionation is that cat head coal mine gas, naphtha fraction, rocket engine fuel cut or diesel oil distillate, tail oil cut are respectively through pipeline 24,25,26,27 caterpillars.
Method provided by the invention adopts expanded bed reactor, alleviates the too fast phenomenon of reactor pressure decrease rising effectively, and the too fast inactivation of inhibited reaction device catalyst at inlet, prolongs on-stream time, can remove nitrogen in the liquefied coal coil simultaneously, improves the liquefied coal coil quality.
The following examples will give further instruction to present method, but therefore not limit present method.
Liquefied coal coil used among the embodiment is through filtering, and the Hydrobon catalyst trade names are RJW-2, are produced by Sinopec Chang Ling catalyst plant.
Embodiment
Test is carried out on medium-sized expanded bed hydrogenation unit.Test raw material is a liquefied coal coil, and stock oil character, processing condition and product property are listed in table 1, table 2 and table 3 respectively.By table as seen, under than the demulcent operational condition, the bromine valency of stabilized hydrogenation product is very low, shows that the alkene major part is by saturated in the liquefied coal coil; The content of product nitrogen and sulphur is low, and boiling range lightens, and has reached the purpose of stabilized hydrogenation.Be 24 months the running period of catalyzer.
Comparative Examples
Test is carried out on medium-sized fixed bed hydrogenation device.Test raw material, processing condition are all identical with embodiment, and under the product property situation close with embodiment, only be 12 months the running period of catalyzer.
The main character of table 1, liquefied coal coil
| Character | Embodiment 1 |
| Density (20 ℃), g/cm 3 | 0.9280 |
| S，m％ | 0.05 |
| N，m％ | 0.22 |
| The bromine valency, gBr/100g | 18.4 |
| Oxygen level, m% | 1.6 |
| Boiling range (ASTM D-1160), ℃ | |
| Initial boiling point | 168 |
| 10％ | 225 |
| 50％ | 301 |
| 95％ | 400 |
Table 2, liquefied coal coil stabilized hydrogenation processing parameter
| Processing condition | Parameter value |
| Temperature of reaction, ℃ | 350 |
| The hydrogen dividing potential drop, MPa | 10.0 |
| Volume space velocity, h -1 | 2.5 |
| Hydrogen-oil ratio, v/v | 700 |
Table 3, liquefied coal coil stabilized hydrogenation product main character
| Product characteristics | Numerical value |
| Density (20 ℃), g/cm 3 | 0.9108 |
| S，ppm | ＜10 |
| N，ppm | 680 |
| The bromine valency, gBr/100g | 2.8 |
| Oxygen level, m% | 0.38 |
| Boiling range (ASTM D-86), ℃ | |
| Initial boiling point | 150 |
| 10％ | 202 |
| 50％ | 279 |
| 95％ | 380 |
Claims (4)
1, a kind of method of liquefied coal coil stabilized hydrogenation is characterized in that liquefied coal coil after filtering, enters expanded bed reactor with hydrogen from reactor bottom, contacts with Hydrobon catalyst, and reactor effluent separates obtaining product through gas-liquid separation, fractionation; Loop back expanded bed reactor from the isolated hydrogen rich stream of high-pressure separator.
2, according to the method for claim 1, it is characterized in that described liquefied coal coil is the product liquid that coal obtains through direct liquefaction, its boiling range is C
5～520 ℃.
3, according to the method for claim 1, it is characterized in that reaction conditions is: hydrogen dividing potential drop 4.0～30.0MPa, 280～450 ℃ of temperature of reaction, liquid hourly space velocity 0.1～10h
-1, hydrogen-oil ratio 300～2800v/v.
4, according to the method for claim 1, it is characterized in that described Hydrobon catalyst is VIA or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, the group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100838984A CN100378201C (en) | 2005-07-15 | 2005-07-15 | Stabilized hydrogenation of coal liquefied oil |
| MYPI20063353 MY150451A (en) | 2005-07-15 | 2006-07-13 | A process for hydro-stabilizing a coal liquefied oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100838984A CN100378201C (en) | 2005-07-15 | 2005-07-15 | Stabilized hydrogenation of coal liquefied oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1896188A true CN1896188A (en) | 2007-01-17 |
| CN100378201C CN100378201C (en) | 2008-04-02 |
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ID=37608838
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100838984A Active CN100378201C (en) | 2005-07-15 | 2005-07-15 | Stabilized hydrogenation of coal liquefied oil |
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| Country | Link |
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| CN (1) | CN100378201C (en) |
| MY (1) | MY150451A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517071A (en) * | 2011-12-26 | 2012-06-27 | 神华集团有限责任公司 | Method for mixing and processing wash oil and direct coal liquefaction oil |
| CN104927897A (en) * | 2014-03-21 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | Direct coal liquefaction oil hydrogenation stabilization method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6190542B1 (en) * | 1996-02-23 | 2001-02-20 | Hydrocarbon Technologies, Inc. | Catalytic multi-stage process for hydroconversion and refining hydrocarbon feeds |
| CN1600837A (en) * | 2003-09-28 | 2005-03-30 | 中国石油化工股份有限公司 | Steady hydrogenation method in counter current of oil liquefied from coal |
-
2005
- 2005-07-15 CN CNB2005100838984A patent/CN100378201C/en active Active
-
2006
- 2006-07-13 MY MYPI20063353 patent/MY150451A/en unknown
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102517071A (en) * | 2011-12-26 | 2012-06-27 | 神华集团有限责任公司 | Method for mixing and processing wash oil and direct coal liquefaction oil |
| CN102517071B (en) * | 2011-12-26 | 2014-04-09 | 神华集团有限责任公司 | Method for mixing and processing wash oil and direct coal liquefaction oil |
| CN104927897A (en) * | 2014-03-21 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | Direct coal liquefaction oil hydrogenation stabilization method |
| CN104927897B (en) * | 2014-03-21 | 2017-10-17 | 湖南长岭石化科技开发有限公司 | A kind of coal direct liquefaction oil stabilized hydrogenation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100378201C (en) | 2008-04-02 |
| MY150451A (en) | 2014-01-30 |
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