CN110240935A - Hydrogenation system and method for hydrotreating - Google Patents
Hydrogenation system and method for hydrotreating Download PDFInfo
- Publication number
- CN110240935A CN110240935A CN201910511888.8A CN201910511888A CN110240935A CN 110240935 A CN110240935 A CN 110240935A CN 201910511888 A CN201910511888 A CN 201910511888A CN 110240935 A CN110240935 A CN 110240935A
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- outlet
- catalyst
- hydrogenation system
- hydrogenating materials
- hydrogenation
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/703—Activation
Abstract
The present invention provides provide a kind of hydrogenation system and method for hydrotreating.The hydrogenation system includes filter, absorber and hydrogenator.Wherein, absorber, which is used to adsorb the impurity in hydrogenating materials, the outlet with filter, and absorber, has hydrogenating materials outlet and spent catalyst inlet；There is hydrogenator hydrogenating materials entrance and dead catalyst to export, hydrogenating materials entrance and hydrogenating materials outlet, spent catalyst inlet and dead catalyst outlet.The method of hydrotreating is filtered processing to raw material the following steps are included: S1, obtains the first processing material；S2 carries out adsorption treatment to the first processing material, obtains second processing material；S3 carries out catalytic hydrogenation reaction to second processing material, and using the dead catalyst after catalytic hydrogenation reaction as recycle stock；S4 repeats step S1 to step S3, and in step s 2, carries out adsorption treatment to the first processing material as adsorbent material using recycle stock.
Description
Technical field
The present invention relates to coal chemical technologies, in particular to a kind of hydrogenation system and method for hydrotreating.
Background technique
DCL/Direct coal liquefaction solvent oil hydrogenation technique can use the boiling bed hydrogenation technology of online displacement catalyst, and raw material be
DCL/Direct coal liquefaction distillate.Carried in raw material coal dust in the distillate containing DCL/Direct coal liquefaction mineral matter element (Fe, Ca,
Na and Mg etc.) and unconverted a small amount of coal dust.After entering distillate hydrogenation reactor, wherein the mineral matter element that carries and
Pulverized coal particle can be attached on catalyst used for hydrogenation of distilled oil fraction (hydrogenation catalyst containing Co, Mo, W, Ni) surface, lead to catalyst
Microcellular structure blocking, cause catalyst activity and selectivity to decline.
In order to guarantee the stabilization of distillate hydrogenation catalyst in reactor activity level, to guarantee product yield and quality,
The frequency that inevitable requirement larger catalyst is replaced online in the prior art drops to be added significantly to the consumption of catalyst
The low cycle of operation of device, and environmental protection pressure is increased because of the processing of waste material and waste water.
In addition, being total in sweetening process in kerosene, metal complex is contained in heavy oil, equally would also adhere to hydrogenation catalyst table
Face, so that catalyst activity be caused to reduce.
Therefore, how to improve in actual production the service efficiency of catalyst be always those skilled in the art target and
Urgent problem to be solved.
Summary of the invention
The main purpose of the present invention is to provide a kind of hydrogenation system and method for hydrotreating, to solve to influence life in the prior art
The efficiency and stability of production pollute the problem of environment and waste catalyst.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of hydrogenation system, comprising: filter,
For filtering the impurity in hydrogenating materials；Absorber, the outlet with filter, for adsorbing the impurity in hydrogenating materials,
And absorber has hydrogenating materials outlet and spent catalyst inlet；Hydrogenator has hydrogenating materials entrance and gives up and urges
Agent outlet, hydrogenating materials entrance and hydrogenating materials outlet, spent catalyst inlet and dead catalyst outlet.
Further, absorber also has spent sorbents outlet, and spent sorbents are exported for drawing off adsorbent material.
Further, hydrogenation system further includes dead catalyst oil removing system, respectively with dead catalyst outlet and dead catalyst
Entrance connection.
Further, hydrogenation system further includes spent sorbents oil removing unit, and spent sorbents oil removing unit goes out with spent sorbents
Mouth is connected.
Further, hydrogenation system further include boosting heat riser, boosting heat riser respectively with hydrogenating materials outlet and
The entrance of hydrogenator is connected to.
Further, hydrogenation system includes multiple absorbers, multiple adsorbers parallel settings.
According to another aspect of the present invention, a kind of method of hydrotreating is provided, comprising the following steps: S1 carried out raw material
Filter processing, obtains the first processing material；S2 carries out adsorption treatment to the first processing material, obtains second processing material；S3 is right
Second processing material carries out catalytic hydrogenation reaction, and using the dead catalyst after catalytic hydrogenation reaction as recycle stock；S4 is repeated
Step S1 to step S3 is executed, and in step s 2, the first processing material is inhaled as adsorbent material using recycle stock
Attached processing.
Further, recycle stock includes dead catalyst and adsorbent.
Further, method of hydrotreating is handled raw material using any hydrogenation system above-mentioned.
It applies the technical scheme of the present invention, provides a kind of hydrogenation system of hydrogenating materials, which includes filtering
Device, absorber and hydrogenator.Wherein, absorber is used to adsorb impurity in hydrogenating materials, the outlet with filter,
And absorber has hydrogenating materials outlet and spent catalyst inlet；Hydrogenator has hydrogenating materials entrance and useless catalysis
Agent outlet, hydrogenating materials entrance and hydrogenating materials outlet, spent catalyst inlet and dead catalyst outlet.Using above-mentioned
Hydrogenation system reduces mineral matter element, pulverized coal particle and metal complex entrained in oil product and can effectively keep away after implementation
The problem of exempting from the microcellular structure blocking due to catalyst and catalyst activity and selectivity is caused to decline, ensure that hydrogenator
The stabilization of interior catalyst activity levels, to guarantee product yield and quality；The service efficiency for improving catalyst, reduces and urges
The frequency of replacement of agent, so that device can be with long-term operation.Also, it by above-mentioned design, can will be in hydrogenator
It is placed in absorber and recycles by the dead catalyst used.
Detailed description of the invention
The Figure of description for constituting a part of the invention is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows a kind of connection relationship diagram of the hydrogenation system of hydrogenating materials provided by the invention.
Wherein, the above drawings include the following reference numerals:
1, filter；2, absorber；3, boost heat riser；4, hydrogenator；5, fractionating system；6, dead catalyst removes
Oil system；7, spent sorbents oil removing unit.
Specific embodiment
It should be noted that in the absence of conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
In order to enable those skilled in the art to better understand the solution of the present invention, below in conjunction in the embodiment of the present invention
Attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The model that the present invention protects all should belong in member's every other embodiment obtained without making creative work
It encloses.
It should be noted that description and claims of this specification and term " first " in above-mentioned attached drawing, "
Two " etc. be to be used to distinguish similar objects, without being used to describe a particular order or precedence order.It should be understood that using in this way
Data be interchangeable under appropriate circumstances, so as to the embodiment of the present invention described herein.In addition, term " includes " and " tool
Have " and their any deformation, it is intended that cover it is non-exclusive include, for example, containing a series of steps or units
Process, method, system, product or equipment those of are not necessarily limited to be clearly listed step or unit, but may include without clear
Other step or units listing to Chu or intrinsic for these process, methods, product or equipment.
As described in background technique, there is efficiency deficiency in the hydrogenation technique of the prior art, and unfavorable
In cost and environmental protection.Present inventor studies regarding to the issue above, propose a kind of hydrogenating materials plus hydrogen
System, as shown in Figure 1, including filter 1, absorber 2 and hydrogenator 4, filter 1 is miscellaneous in hydrogenating materials for filtering
Matter；The outlet of absorber 2 and filter 1, for adsorbing the impurity in hydrogenating materials, and absorber 2 has hydrogenating materials
Outlet and spent catalyst inlet；There is hydrogenator 4 hydrogenating materials entrance and dead catalyst to export, hydrogenating materials entrance
With hydrogenating materials outlet, spent catalyst inlet and dead catalyst outlet.
Mineral matter element, pulverized coal particle and metal complex entrained in oil product are reduced using above-mentioned hydrogenation system,
After implementation, it can effectively avoid the microcellular structure blocking due to catalyst and cause asking for catalyst activity and selectivity decline
Topic, ensure that the stabilization of catalyst activity levels in hydrogenator, to guarantee product yield and quality；Also, pass through by
It is placed in absorber and recycles by the dead catalyst used in hydrogenator, improve the service efficiency of catalyst, drop
The low frequency of replacement of catalyst, so that device can be with long-term operation.
In above-mentioned hydrogenation system of the invention, the adsorbent material in absorber 2 includes adsorbent and dead catalyst, can be with
Effectively adsorb mineral matter element, pulverized coal particle and metal complex entrained in oil product.Absorber 2 can also have useless suction
Attached dose of outlet, spent sorbents are exported for drawing off adsorbent material.Also, absorber 2 can be made of multi-series, e.g. in parallel
The multiple absorbers 2 being arranged can mutually switch use.
In above-mentioned hydrogenation system of the invention, filter 1 can also include its corresponding flushing and regeneration with absorber 2
Unit.
Preferably, the hydrogenation system of the hydrogenating materials includes dead catalyst oil removing system 6.Hydrogenator 4 has first
Outlet, dead catalyst enter dead catalyst oil removing system 6 after drawing off from the first outlet of hydrogenator 4 and carry out de-oiling, then
Absorber 2 is entered by spent catalyst inlet again.It can be recycled via the waste oil of 6 de-oiling of dead catalyst oil removing system.
Preferably, the hydrogenation system of the hydrogenating materials includes spent sorbents oil removing unit 7.Spent sorbents go out from spent sorbents
Mouth enters spent sorbents oil removing unit 7 after drawing off and carries out de-oiling.Spent sorbents oil removing unit 7 can pack spent sorbents de-oiling,
And recycle waste oil.
Preferably, the hydrogenation system of the hydrogenating materials includes boosting heat riser 3.Hydrogenating materials are entering hydrogenator
Boosting heating is carried out by the heat riser 3 that boosts before 4.Above-mentioned hydrogenator 4 also have second outlet, the second outlet with point
Evaporate the connection of system 5.
Above-mentioned hydrogenation system of the invention is suitable for inferior heavy oil, viscous crude and containing solid feedstock oil hydrotreating and is hydrocracked
Technique refines hydrogenation technique especially suitable for DCL/Direct coal liquefaction distillate hydrogenation technique and kerosene altogether.
According to another aspect of the present invention, a kind of method of hydrotreating is additionally provided, comprising the following steps: S1 carries out raw material
Filtration treatment obtains the first processing material；S2 carries out adsorption treatment to the first processing material, obtains second processing material；S3,
Catalytic hydrogenation reaction is carried out to second processing material, and using the dead catalyst after catalytic hydrogenation reaction as recycle stock；S4, weight
Step S1 to step S3 is executed again, and in step s 2, the first processing material is carried out as adsorbent material using recycle stock
Adsorption treatment.
Mineral matter element, pulverized coal particle and metal complex entrained in oil product are reduced using above-mentioned method of hydrotreating,
After implementation, it can effectively avoid the microcellular structure blocking due to catalyst and cause asking for catalyst activity and selectivity decline
Topic, ensure that the stabilization of catalyst activity levels in hydrogenator, to guarantee product yield and quality；Improve catalyst
Service efficiency, the frequency of replacement of catalyst is reduced, so that device can be with long-term operation.
In above-mentioned steps S4, it is preferable that recycle stock includes above-mentioned dead catalyst and adsorbent.
In a preferred embodiment, raw material is handled using above-mentioned hydrogenation system.
Above-mentioned method of hydrotreating of the invention is suitable for inferior heavy oil, viscous crude and containing solid feedstock oil hydrotreating and is hydrocracked
Technique refines hydrogenation technique especially suitable for DCL/Direct coal liquefaction distillate hydrogenation technique and kerosene altogether.
Above-mentioned method of hydrotreating is by 40 ton/hours of liquefied coal coils of processing, 436 ton/hours of design charging, catalyst on-stream cycle time
Interior 640 tons of consumption, catalyst unit price account for charge proportion by 130,000 yuan/ton of calculating, filtration yield: 40/436=0.0917, it is assumed that can
Influence of the oil product to catalyst life can save catalytic amount then within the former cycle of operation as 0.0917*640 after ignoring filtering
=58.72 tons, being worth is ten thousand yuan of 58.72*13=763 (763 Wan Yuanli do not deduct the depreciation of device, artificial, operating cost etc.).
The present invention at home and abroad temporarily can not be substituted scheme at present.
Hydrogenation system and its method of hydrotreating provided by the invention are further illustrated below in conjunction with embodiment.
Embodiment 1
The project scale of device is 330 × 104Ton/year, year operates 7440 hours, and practical charging is coal liquefaction heavy oil 436
Ton/hour, 427 kgs/hr of coal liquefaction light oil, boiling range is 164-470 DEG C, coal dust content 0.01%-0.15%；Metal contains
Total content≤the 30mg/kg of amount, i.e. iron, calcium, sodium and magnesium；Filter Precision is 180 microns；Two absorbers are set, are switched
Period be 90 days, about 20 tons of the adsorbent inventory of every absorber (wherein about 7 tons of Special adsorbent, complementary space load by
The dead catalyst that hydrogenator is drawn off), handle 40 ton/hours of coal liquefaction heavy oil amount；1.2 ton/days of discharged amount of catalyst day, fortune
58.72 tons of catalyst can be saved in the row period.
Filling scheme from the adsorbent of absorber and the analysis for drawing off rear adsorbent, adsorbent is with preferable demetalization
With the miscellaneous ability of appearance, a large amount of quality raw materials are provided to coal liquefaction stabilized hydrogenation unit, have been provided to produce high-quality solvent naphtha
Sharp condition provides advantageous space to improve liquiefied product quality, oil yield and working ability.Hydrogen is added by using of the invention
System slows down the frequency of replacement of correlation unit significantly, reduces since ammonia salt crystallization results in blockage and corrodes, to make coal liquefaction
Equipment safety, stabilization, long-acting and high-quality operating provide very favorable condition, and then improve the whole economic efficiency of production,
Add up in the former cycle of operation and save about 7,630,000 yuan, while reducing spent catalyst (including porcelain ball) discharge hundredweight/year, reduces
60 tons/year of the sewage discharge of flour containing catalyst, reduces environmental improvement expense, alleviates environmental protection pressure.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
1, mineral matter element, pulverized coal particle and gold entrained in oil product can be reduced as adsorbent using dead catalyst
Belong to complex compound, after implementation, can effectively avoid the microcellular structure blocking due to catalyst and cause catalyst activity and selectivity
The problem of decline, it ensure that the stabilization of catalyst activity levels in hydrogenator, to guarantee product yield and quality；
2, the service efficiency for improving catalyst reduces the frequency of replacement of catalyst, so that device can be transported with long period
Row；
3, reduce catalyst consumption, save the cost, and be conducive to environmental protection.
The foregoing is merely the preferred embodiment of the present invention, are not intended to restrict the invention, for this field
For technical staff, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any
Modification, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of hydrogenation system characterized by comprising
Filter (1), for filtering the impurity in hydrogenating materials；
Absorber (2), the outlet with the filter (1), for adsorbing the impurity in the hydrogenating materials, and the suction
Adnexa (2) has hydrogenating materials outlet and spent catalyst inlet；
There is hydrogenator (4) hydrogenating materials entrance and dead catalyst to export, the hydrogenating materials entrance and described plus hydrogen
Material outlet connection, the spent catalyst inlet and the dead catalyst outlet.
2. hydrogenation system according to claim 1, which is characterized in that the absorber (2) also has spent sorbents outlet,
The spent sorbents outlet is for drawing off adsorbent material.
3. hydrogenation system according to claim 1, which is characterized in that the hydrogenation system further include:
Dead catalyst oil removing system (6) is connected to dead catalyst outlet and the spent catalyst inlet respectively.
4. hydrogenation system according to claim 2, which is characterized in that the hydrogenation system further includes spent sorbents oil removing list
First (7), the spent sorbents oil removing unit (7) are connected with spent sorbents outlet.
5. hydrogenation system according to any one of claim 1 to 4, which is characterized in that the hydrogenation system further includes rising
Press heat riser (3), boosting heat riser (3) respectively with hydrogenating materials outlet and the hydrogenator (4)
Entrance connection.
6. hydrogenation system according to any one of claim 1 to 4, which is characterized in that the hydrogenation system includes multiple
The absorber (2), multiple absorbers (2) are arranged in parallel.
7. a kind of method of hydrotreating, which comprises the following steps:
S1 is filtered processing to raw material, obtains the first processing material；
S2 carries out adsorption treatment to the first processing material, obtains second processing material；
S3 carries out catalytic hydrogenation reaction to the second processing material, and the dead catalyst after the catalytic hydrogenation reaction is made
For recycle stock；
S4 repeats the step S1 to the step S3, and in the step S2, using the recycle stock as suction
Enclosure material carries out adsorption treatment to the first processing material.
8. method of hydrotreating according to claim 7, which is characterized in that the recycle stock includes the dead catalyst and suction
Attached dose.
9. the method for hydrotreating according to any one of claim 7 or 8, which is characterized in that the method for hydrotreating uses right
It is required that hydrogenation system described in any one of 1 to 6 handles the raw material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910511888.8A CN110240935A (en) | 2019-06-13 | 2019-06-13 | Hydrogenation system and method for hydrotreating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910511888.8A CN110240935A (en) | 2019-06-13 | 2019-06-13 | Hydrogenation system and method for hydrotreating |
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| Publication Number | Publication Date |
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| CN110240935A true CN110240935A (en) | 2019-09-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201910511888.8A Pending CN110240935A (en) | 2019-06-13 | 2019-06-13 | Hydrogenation system and method for hydrotreating |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458245A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Paraffin adsorption refining method |
| CN101041789A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Waste lubricating oil hydrogenation reproducing method |
-
2019
- 2019-06-13 CN CN201910511888.8A patent/CN110240935A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1458245A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Paraffin adsorption refining method |
| CN101041789A (en) * | 2007-04-30 | 2007-09-26 | 京福马(北京)石油化工高新技术有限公司 | Waste lubricating oil hydrogenation reproducing method |
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