CN109701668A - The method of vulcanization that hydrogenation plant goes into operation the on-line control system of vulcanization and On-line Control hydrogenation plant goes into operation - Google Patents
The method of vulcanization that hydrogenation plant goes into operation the on-line control system of vulcanization and On-line Control hydrogenation plant goes into operation Download PDFInfo
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Abstract
The present invention relates to catalyst vulcanizations to restore field, discloses that hydrogenation plant goes into operation the on-line control system of vulcanization and On-line Control hydrogenation plant goes into operation the method for vulcanization, which contains: hydrogen sulfide on-line checking analysis module；Reaction bed temperature detection module；Vulcanizing agent flow-control module；Central control module, the instruction that vulcanizing agent injects changes in flow rate is issued to the vulcanizing agent flow-control module for comparing the temperature of the concentration of hydrogen sulfide being collected by the hydrogen sulfide on-line checking analysis module with the catalyst bed being collected by the reaction bed temperature detection module, and according to comparison result.The system can carry out as required presulfiding of catalyst on the basis of oil plant existing apparatus, simplify the operation of pre-vulcanization process, human cost is saved, keep pre-vulcanization process heating steady, concentration of hydrogen sulfide is controlled in zone of reasonableness, is reduced the usage amount of vulcanizing agent, is improved efficiency, operating cost is reduced, and has saved the energy.
Description
Technical field
The present invention relates to catalyst vulcanizations to restore field, and in particular to a kind of hydrogenation plant goes into operation the On-line Control system of vulcanization
System and a kind of application on-line control system On-line Control hydrogenation plant go into operation the method for vulcanization.
Background technique
It is increasingly strict with crude resources in poor quality in world wide and environmental regulation, it needs to give birth under severe conditions
Produce a large amount of good clean fuels.The environmentally friendly property that can be good at improving oil product by the hydrotreating to oil product, keeps its right
Environment more optimizes, and therefore, fixed bed hydrogenation technology has obtained increasingly extensive application.
Fixed bed hydrogenation processing catalyst is generally the catalyst of oxidation state, active metal (generally cobalt, molybdenum, nickel,
Tungsten) using oxidation states as commodity selling, it needs to carry out presulfurization processing to it before use, i.e., by oxidation state active metal
It is converted into corresponding sulphided state metal, to reach good catalyst activity.
Fixed bed hydrogenation catalyst generallys use in-situ presulfurization technology, which is divided into the vulcanization of dry pre-sulfiding and wet process.
It is dry pre-sulfiding, as the term suggests it is also using rich in hydrogen sulfide for the vulcanization that no liquid phase moistens oxidized catalyst and carries out
Hydrogen vulcanized in gas phase atmosphere；Wet process vulcanization is in the presence of having liquid phase, and oxidized catalyst is passed through
Vulcanization reaction occurs for the vulcanizing agent carried after wetting with sulfurized oil.
Wet process sulfidation needs inject vulcanizing agent in sulfurized oil, vulcanizing agent certain hydrogen partial pressure and at a temperature of face hydrogen
It decomposes and generates H2S, H2S is converted to respective metal sulfide with reactive metal oxide on catalyst.Vulcanizing agent generally uses diformazan
Two sulphur of base (DMDS), carbon disulfide (CS2) etc. a series of organic sulfur compounds.
The pre-vulcanization process of catalyst be make vulcanizing agent decomposed in the case where facing hydrogen state production hydrogen sulfide, hydrogen sulfide again with catalysis
The active metal component of agent reacts, and is translated into the process of sulphided state.The reaction process of sulfidation can be expressed as follows:
(CH3)2S2Or CS2+3H2→2H2S+2CH4
MoO3+2H2S+H2→MoS2+3H2O
NiO+H2S→NiS+H2O or
3NiO+2H2S+H2→Ni3S2+3H2O
It is dry pre-sulfiding because its vulcanization after need and reaction bed temperature be reduced to safe temperature when just introduce low nitrogen
The oil that goes into operation carries out catalyst irrigation, then carries out heating again and gradually switches feedstock oil.On-stream time is longer, completely smoothly
Under the premise of need 6 days or more time, and be prone to the detrimental effects such as larger temperature fluctuation.
Most of presulfurization in industrial fixed bed hydrogenation processing unit start-up process is vulcanized using wet process, and the time is longer
And there is step not easy to control in the process.It is typically chosen carrying oil of the light-end products as vulcanizing agent.In pre-vulcanization process
Primary starting recycle hydrogen ring machine and feedstock oil feed pump allow vulcanization to carry oil together with recycle hydrogen in the Catalyst packing of oxidation state
Circulation in reactor.It is warming up to after the decomposition temperature of vulcanizing agent and exports injection vulcanizing agent in feedstock oil surge tank with centrifugal pump, allow
Vulcanization carrying oil is brought into reactor bed and is vulcanized.
The end mark of wet process vulcanization are as follows: presulfurization reaches the final regulation constant temperature of vulcanization, and has continued constant temperature regulation
Time is longer；Hydrogen sulfide volume fraction is more than 1% in recycle hydrogen；There is no water generation, high score or low point are put not twice in succession
Water outlet；Concentration of hydrogen sulfide does not decline or declines and is very slow in the recycle hydrogen of stopping injection vulcanizing agent back end hydrogenation device.
There are several key points, first key point in wet process sulfidation are as follows: it heats up before 230 DEG C after vulcanization oil inlet,
Hydrogen sulfide volume fraction in oxidized catalyst bed must be over 0.1%.It otherwise can be because concentration of hydrogen sulfide be in recycle hydrogen
It is enough, continue to heat up and active metal in oxidized catalyst is caused finally to lose catalyst by hydrogen reducing, aggregation, hardened
Go corresponding activity.Second key point are as follows: before 230 DEG C to final curing temperature (generally 320 DEG C), in this temperature
Section is spent, several generation vulcanization reaction stages are belonged to for oxidized catalyst, need to consume a large amount of hydrogen sulfide, and guarantee
Good vulcanization effect needs in control loop hydrogen hydrogen sulfide volume fraction 0.5~1.0%.Wet process vulcanization at present is logical
The injection rate of vulcanizing agent is turned down by experience or be turned up to the height for the concentration of hydrogen sulfide crossed in on-site test recycle hydrogen.
Concentration of hydrogen sulfide detection in sulfidation in live recycle hydrogen, needs by being acquired with bladders or steel cylinder
Recycle hydrogen gas.Sulfurated hydrogen detection pipe is used when detecting concentration of hydrogen sulfide, the gas sample of acquisition is injected by vulcanization using syringe
In hydrogen detection pipe.This not only causes rich hydrogen sulfide containing gas to the harm of worker's personal safety but also right to a certain extent
Environment also results in destruction.
The testing principle of sulfurated hydrogen detection pipe is will to adsorb lead acetate (PbAC2) and barium chloride (BaCl2) silica gel be packed into it is thin
In glass tube, the hydrogen sulfide containing gas of 100ml is taken out, is injected in detection pipe in 60s, brown vulcanization is formed by observation silicagel column
The length of lead (PbS) reads the registration in detection pipe, to measure the volume fraction of vulcanization.The method have it is easy, quick,
The advantages of easy to carry and high sensitivity.But detection needs the regular hour, and tester has certain professional knowledge,
It needs to wear ventilator and has care provider.But occasion higher for concentration of hydrogen sulfide is unsuitable.
The prevention and treatment of hydrogen sulfide poisoning becomes the important topic that enterprise carries out occupation health safety work.In recent years, pass through political affairs
The effort of the mechanisms such as mansion, enterprise, medical treatment and scientific research, hydrogen sulfide poisoning prevention and treatment achieve certain effect, but hydrogen sulfide poisoning thing
Part still occurs in oil refining enterprise, particularly in oil refining enterprise in vulcanization start-up process.Because during catalyst vulcanization
The concentration for needing to monitor hydrogen sulfide, need the gas by the concentration of hydrogen sulfide rich in high concentration in process pipelines produce into
Row analysis, the sulfurated hydrogen detection pipe that field assay uses.There is a certain security risk for these operations, is easy to cause sampling people
Sulfur poisoning occurs for member, field assay testing staff.Therefore, it is monitored for the concentration of hydrogen sulfide in the sulfidation that goes into operation at present,
It is imperative using the sulfurated hydrogen detection system of real-time online.
Hydrogen sulfide is a kind of hypertoxic gas of colourless, rotten smell of putrid egg, and concentration of hydrogen sulfide is in 375~750mg/m3When, contact
Pulmonary edema and central nervous system symptom and the loss of consciousness or even respiratory failure can occur within 0.5~1 hour；Concentration of hydrogen sulfide
For 1000mg/m3When sucking the several seconds can occur sudden death i.e. shock by electricity sample it is dead.
Circulation hydrogen concentration in sulfidation is generally 5000~20000mg/m3, the recycle hydrogen gas of such high concentration is logical
Over-sampling detection bring the huge security risk of operator, such operation should be avoided from process safety, without device outside
Sampling analysis.
CN102049318A discloses a kind of vulcanizing agent supply method of catalyst wet sulfidation.What this method used
It is directly to allow hydrogen and vulcanizing agent to generate in reactor in hydrogen sulfide to be reacted, the hydrogen sulfide of generation is directly injected into circulation
In hydrogen.This method be suitable for liquid-phase hydrogenatin device go into operation sulfidation because dissolve amounts of hydrogen it is insufficient due to cause vulcanizing agent to decompose speed
Spend slow problem.There is still a need for carry out detection concentration of hydrogen sulfide, the decomposition rate of manual de-regulation hydrogen sulfide generator to this method.
US6248687B1 discloses a kind of hydrogenation catalyst presulfurizing method.The characteristics of this method is by sulfurized oil
Middle addition 0.1 weight % or so macromolecular, organic sulfur compound containing multiple sulphur atoms, can significantly improve the generation of hydrogen sulfide
Amount, is conducive to catalyst vulcanization.
CN102942957A discloses a kind of Presulfuration technology of hydrogenation unit.The process requirement is a set of to be added different from presulfurization
The hydrogenation plant of hydrogen production device is used as non-desulphurization circulating hydrogen feeding mechanism, its rich hydrogen sulfide containing hydrogen is passed through presulfurization, hydrogen is added to fill
Set carry out presulfiding of catalyst.The technique need not use vulcanizing agent, therefore effectively avoid injury of the toxic vulcanizing agent to operative employee
With the pollution to environment.
Summary of the invention
It goes into operation the on-line control system of vulcanization the object of the present invention is to provide a kind of hydrogenation plant, which can refine oil
Presulfiding of catalyst is carried out on the basis of factory's existing apparatus as required, the operation of pre-vulcanization process is simplified, has saved manpower
Cost keeps pre-vulcanization process heating steady, and concentration of hydrogen sulfide is controlled in zone of reasonableness, reduces the usage amount of vulcanizing agent, improves
Efficiency, reduces operating cost, and saved the energy.
To achieve the goals above, the first aspect of the present invention provides the On-line Control system that a kind of hydrogenation plant goes into operation vulcanization
It unites, contains in the on-line control system:
(1) hydrogen sulfide on-line checking analysis module adds catalyst progress presulfurization processing for acquiring and analyzing
Concentration of hydrogen sulfide in the recycle hydrogen of hydrogen production device；
(2) reaction bed temperature detection module, for detecting and acquiring the catalyst bed of the hydrogenation plant
Temperature；
(3) vulcanizing agent flow-control module, for controlling the flow for the vulcanizing agent being introduced in the hydrogenation plant；
(4) central control module is dense for comparing the hydrogen sulfide being collected by the hydrogen sulfide on-line checking analysis module
Degree and the temperature of catalyst bed being collected by the reaction bed temperature detection module, and according to comparison result to institute
State the instruction that vulcanizing agent flow-control module issues vulcanizing agent injection changes in flow rate.
The second aspect of the present invention provides a kind of method that On-line Control hydrogenation plant goes into operation vulcanization, and this method is before containing
State hydrogenation plant described in first aspect go into operation vulcanization on-line control system device in carry out, this method comprises:
(1) by after heating sulfurized oil and vulcanizing agent and recycle hydrogen be concomitantly introduced into the catalyst bed of hydrogenation plant with
Vulcanizing treatment is carried out to the oxidized catalyst contained in the catalyst bed；
(2) material obtained after the vulcanizing treatment gas-liquid separator is introduced to separate, obtain gaseous component and
Liquid phase component；
(3) obtain recycle hydrogen after being settled the gaseous component, and by the recycle hydrogen and new hydrogen be concomitantly introduced into
In circulating hydrogen compressor；The liquid phase component is recycled back in step (1) simultaneously；
Wherein, in the on-line control system that the hydrogenation plant goes into operation vulcanization, hydrogen sulfide on-line checking analysis module is adopted
Collection and analyze to the concentration of hydrogen sulfide in the recycle hydrogen of the hydrogenation plant, the detection of reaction bed temperature detection module and
The temperature of the catalyst bed of the hydrogenation plant is acquired, central control module, which is compared, analyzes mould by the hydrogen sulfide on-line checking
The temperature of the concentration of hydrogen sulfide that block is collected into and the catalyst bed being collected by the reaction bed temperature detection module, and
And the instruction of vulcanizing agent injection changes in flow rate is issued to vulcanizing agent flow-control module according to comparison result.
On-line control system provided by the invention, directly by recycle hydrogen gas using hydrogen sulfide on-line checking analysis module into
Row detection, the gas after detection are discharged into exhaust pipe after treatment or carry out lye absorption, avoid frequently sampling and make
At hazardous gas security hidden danger.
The on-line control system that this method provides, the catalyst bed transmitted by reaction bed temperature detection module
Temperature, and judged concentration of hydrogen sulfide and curing curve data by central control module, to provide note sulphur pump
Injection rate.The on-line control system realizes situ vulcanized hydrogen detection, analysis, infuses and control operation in the integration of sulphur rate adaptation,
It is fully able to realize unattended, greatly improves the working environment for the vulcanization that goes into operation, realize being free from risk for hydrogen sulfide prevention and treatment.
Detailed description of the invention
Fig. 1 is a kind of schematic diagram of hydrogenation plant vulcanization start-up process provided by the invention.
Description of symbols
1, head tank 2, raw material pump
3, vulcanizing agent tank 5, vulcanizing agent supply pump
8, heating furnace 10, new hydrogen
11, circulating hydrogen compressor 12, catalyst bed
14, gas-liquid separator 19, hydrogen sulfide on-line checking analysis module
20, first data transmission line 21, the second data line
22, central control module 23, third data line
24, settling tank
4,6,7,9,13,15,16,17,18 be pipeline.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
It goes into operation the on-line control system of vulcanization as previously mentioned, the first aspect of the present invention provides a kind of hydrogenation plant, it should
Contain in on-line control system:
(1) hydrogen sulfide on-line checking analysis module adds catalyst progress presulfurization processing for acquiring and analyzing
Concentration of hydrogen sulfide in the recycle hydrogen of hydrogen production device；
(2) reaction bed temperature detection module, for detecting and acquiring the catalyst bed of the hydrogenation plant
Temperature；
(3) vulcanizing agent flow-control module, for controlling the flow for the vulcanizing agent being introduced in the hydrogenation plant；
(4) central control module is dense for comparing the hydrogen sulfide being collected by the hydrogen sulfide on-line checking analysis module
Degree and the temperature of catalyst bed being collected by the reaction bed temperature detection module, and according to comparison result to institute
State the instruction that vulcanizing agent flow-control module issues vulcanizing agent injection changes in flow rate.
Under preferable case, what the hydrogen sulfide on-line checking analysis module acquired is the circulation hydrogen compressed of the hydrogenation plant
Concentration of hydrogen sulfide in the hydrogen of machine entrance.That is, the recycle hydrogen of the invention comes from circulating hydrogen compressor under preferable case
Before, it is not yet mixed with new hydrogen.
Preferably, DCS (Distributed Control System) unit, the reaction bed temperature detection are contained in the hydrogenation plant
The temperature data of catalyst bed is transferred to the DCS unit by module, and the central control module and the DCS are serviced
Device carries out data interaction.
Preferably, the hydrogen sulfide on-line checking analysis module is to gather the combination of the sensor of sulfurated hydrogen detection and analysis
Or concentration of hydrogen sulfide on-line detector.The concentration of hydrogen sulfide on-line detector can for commercialization to be able to detect hydrogen sulfide dense
The instrument of degree.
Preferably, vulcanizing agent supply pump is contained in the vulcanizing agent flow-control module, the vulcanizing agent supply pump is used for
Realize the variation of the injection flow of vulcanizing agent in the hydrogenation plant.The flow of the vulcanizing agent supply pump is controlled by the center
Module is controlled according to reaction bed temperature and concentration of hydrogen sulfide.
Preferable case, the hydrogenation plant is that vapour-liquid consolidates hydrogenation plant or liquid-phase hydrogenatin device.
Under preferable case, hydrogen sulfide treatment module is also contained in on-line control system of the invention, is used for the vulcanization
Hydrogen sulfide after hydrogen on-line checking analysis module is acquired and analyzed in recycle hydrogen gas carries out exhaust-gas treatment.
The central control module of the invention is data collection, storage, analysis, computing module, can be PC host, clothes
A series of electronic computers with the above function such as business device, single-chip microcontroller.
The DCS unit of the invention, as the DCS server host of hydrogenation plant, wherein containing catalyst bed temperature
Detection module is spent, the temperature data of catalyst bed, also, the central control module can be provided for central control module
There is level-one priority higher than DCS unit in the temperature control of catalyst bed.
It goes into operation the method for vulcanization as previously mentioned, the second aspect of the present invention provides a kind of On-line Control hydrogenation plant, it should
Method carries out in the device of the on-line control system for the vulcanization that goes into operation containing hydrogenation plant described in aforementioned first aspect of the present invention,
This method comprises:
(1) by after heating sulfurized oil and vulcanizing agent and recycle hydrogen be concomitantly introduced into the catalyst bed of hydrogenation plant with
Vulcanizing treatment is carried out to the oxidized catalyst contained in the catalyst bed；
(2) material obtained after the vulcanizing treatment gas-liquid separator is introduced to separate, obtain gaseous component and
Liquid phase component；
(3) obtain recycle hydrogen after being settled the gaseous component, and by the recycle hydrogen and new hydrogen be concomitantly introduced into
In circulating hydrogen compressor；The liquid phase component is recycled back in step (1) simultaneously；
Wherein, in the on-line control system that the hydrogenation plant goes into operation vulcanization, hydrogen sulfide on-line checking analysis module is adopted
Collection and analyze to the concentration of hydrogen sulfide in the recycle hydrogen of the hydrogenation plant, the detection of reaction bed temperature detection module and
The temperature of the catalyst bed of the hydrogenation plant is acquired, central control module, which is compared, analyzes mould by the hydrogen sulfide on-line checking
The temperature of the concentration of hydrogen sulfide that block is collected into and the catalyst bed being collected by the reaction bed temperature detection module, and
And the instruction of vulcanizing agent injection changes in flow rate is issued to vulcanizing agent flow-control module according to comparison result.
Preferably, the vulcanizing agent is inorganic sulphide and/or organic sulfur compound.It is highly preferred that the vulcanizing agent is selected from
In hydrogen sulfide, carbon disulfide, mercaptan, thiophene and derivatives, dialkyl sulfide, dimethylsulphide and dimethyl sulfide
It is at least one.
Preferably, the sulfurized oil is petroleum distillate of the boiling range within the scope of 180~400 DEG C.It is highly preferred that the vulcanization
Oil in kerosene, normal two wires distillate, atmosphere 3rd side cut distillate, catalytic cracking diesel oil, straight-run diesel oil and coker gas oil at least
It is a kind of；It is particularly preferred that the sulfurized oil is straight-run diesel oil and/or kerosene.
Under preferable case, carrier and hydrogenation active metal component are contained in the oxidized catalyst, and optionally contain
Auxiliary element；The carrier is selected from least one of aluminium oxide, silica and aluminium oxide-silicon oxide, the hydrogenation activity gold
Category group is selected from least one of group VIB and group VIII metallic element；The auxiliary element is in phosphorus, fluorine and boron
It is at least one；It is highly preferred that the hydrogenation active metal component is selected from least one of molybdenum, tungsten, cobalt and nickel metallic element.
Carrier in the oxidized catalyst of the invention can be heat-resisting porous material.
In the method for the invention, the oil circuit in the sulfidation processes can be closed cycle, and sulfurized oil can come
It from material tank, is mixed before being heated into heating furnace with vulcanizing agent, then enters back into the catalyst bed of hydrogenation plant.
In the method for the invention, the temperature of the catalyst bed in the preferably described hydrogenation plant is 150~400 DEG C.
There is no particular limitation to specific vulcanizing treatment step and parameter for method of the invention, can for it is in the art often
The vulcanizing treatment step and parameter for advising application illustratively give vulcanizing treatment step and parameter in the embodiment of the present invention
Example, those skilled in the art should not be construed as limiting the invention.
A kind of hydrogenation plant vulcanization start-up process is provided below in conjunction with Fig. 1 to illustrate that hydrogenation plant of the invention goes into operation vulcanization
On-line control system and On-line Control hydrogenation plant go into operation the method for vulcanization.Many equipment are omitted in figure, such as pump, heat exchanger
Deng, but this is well known to those of ordinary skill in the art.
Sulfurized oil from head tank 1 is delivered to pipeline 7 by raw material pump 2, and the vulcanizing agent from vulcanizing agent tank 3 passes through pipe
Line 4 enters vulcanizing agent supply pump 5, and is delivered to pipeline 6 by vulcanizing agent supply pump 5.Sulfurized oil and vulcanizing agent are into heating furnace 8
It is mixed, drawn after the heating of heating furnace 8 by pipeline 9 and is mixed with the recycle hydrogen from circulating hydrogen compressor 11 before
It closes, subsequently into the catalyst bed 12 containing oxidized catalyst, is introduced by the logistics of catalyst bed by pipeline 13
Gas-liquid separator 14, isolated gaseous component enter settling tank 24 through pipeline 15.The isolated recycle hydrogen of settling tank 24
Enter circulating hydrogen compressor 11 after mixing with the new hydrogen 10 in part.The liquid phase component of 14 bottom of gas-liquid separator is recycled back to through pipeline 16
Into head tank 1, pipeline 17 is the pipeline conveyed under nominal situation to subsequent separation system.Hydrogen sulfide on-line checking analysis module
19 by by pipeline 18 come recycle hydrogen acquire and analyze hydrogen sulfide volume fraction therein, obtained data pass through the first data
Transmission line 20 inputs central control module 22, and the temperature of catalyst bed is by the catalysis in the DCS server of hydrogenation plant itself
The acquisition of agent bed temperature detection module and analysis, and the central control module 22 and the DCS server pass through second
Data line 21 carries out data interaction, and central control module 22 is according to the comparison of the temperature of concentration of hydrogen sulfide and catalyst bed
As a result the instruction of vulcanizing agent injection changes in flow rate is issued from third data line 23 to vulcanizing agent flow-control module.
Preceding method provided by the invention and system also have the advantages that following specific:
(1) present invention realizes that hydrogenation plant presulfurization is not necessarily to carry out hydrogen sulfide artificial sample during the vulcanization that goes into operation, effectively
Toxic hydrogen sulfide is avoided to injure caused by operative employee and environmental pollution.
(2) this invention simplifies the operation of pre-vulcanization process, human cost has been saved, has kept pre-vulcanization process heating steady,
The feedback mechanism for setting up the usage amount of concentration of hydrogen sulfide and vulcanizing agent, improves efficiency, reduces operating cost, and save
The energy.
(3) present invention can be carried out catalyst using the technique of safety and environmental protection under the premise of using vulcanizing agent less as far as possible
Complete cure.And vulcanized in sulfidation by the injection rate of vulcanizing agent come the concentration of hydrogen sulfide in control system with matching
Heating curve.
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment is carried out using process flow shown in FIG. 1, the sulfidation of oxidized catalyst in hydrogenation plant:
The W-Co- of the RS series of Research Institute of Petro-Chemical Engineering's development and production is loaded in medium-sized hydrogenation test apparatus reactor
Ni system Hydrobon catalyst, catalyst physico-chemical property are shown in Table 1.Vulcanizing agent uses CS2.Recycle hydrogen is detected when operation first
Middle H2The concentration of S, then judge whether concentration required by matching the vulcanization heating curve of catalyst, further by adjusting note sulphur
The note sulphur rate of pump.
When catalyst bed is 150 DEG C, fresh hydrogen is pressurized to after 6.4MPa enters catalyst bed with sulfurized oil together
Layer.175 DEG C are warming up to 15 DEG C/h, while opening on-line control system, starts real-time detection concentration of hydrogen sulfide, and start to inject
Vulcanizing agent.230 DEG C are warming up to 15 DEG C/h, is started constant temperature 6 hours.320 DEG C are warming up to 15 DEG C/h after constant temperature, is started permanent
Temperature 8 hours.The concentration of hydrogen sulfide in each stage requires to be shown in Table 2.
After vulcanization, 320 DEG C are warming up to, uses straight-run diesel oil for feedstock oil, adjusting process condition, after stablizing 48 hours
Sampling analysis catalyst desulfurizing performance, concrete technology condition are shown in Table 3.
In order to investigate catalyst vulcanization effect, 20 weight % catalytic diesel oils of refining are mixed using straight-run diesel oil and carry out catalyst as raw material
Activity rating, evaluation condition and raw material oil nature are shown in Table 4.
Comparative example 1
This comparative example uses process and condition similar to Example 1, the difference is that on-line control system is not used,
It acquires recycle hydrogen gas manually using operative employee, analyzes wherein concentration of hydrogen sulfide, and the hydrogen sulfide according to as defined in curing curve is dense
Degree manually adjusts the injection rate of vulcanizing agent.
As a result as shown in table 4.
Table 1
| Catalyst | RS series |
| Chemical composition, weight % | |
| WO3 | ≥26 |
| NiO | ≥2.6 |
| MoO3 | 2.3 |
| Physical property | |
| Specific surface, m2/g | ≥130 |
| Kong Rong, mL/g | ≥0.20 |
| Shape | Clover |
Table 2
| Sulfurating stage | H2S/ (volume %) |
| 150 DEG C of oil inlet constant temperature | - |
| 175℃ | -3 |
| 175~230 DEG C of heatings | 0.3 |
| 230 DEG C of constant temperature | 0.5 |
| 230~320 DEG C | 1.0 |
| 320 DEG C of constant temperature | 1.5 |
Table 3
| Process conditions | Embodiment 1 |
| Feedstock oil | Straight-run diesel oil |
| Reaction temperature/DEG C | 320 |
| Hydrogen partial pressure/MPa | 6.4 |
| Standard state hydrogen to oil volume ratio | 300 |
| Volume space velocity/h-1 | 1.5 |
Table 4
Find out from 4 result of table, using on-line control system, the activity after catalyst vulcanization is better than conventional catalyst sulphur
Change.Vulcanization time is obviously shortened simultaneously, and the usage amount of vulcanizing agent is than the conventional dosage for reducing by 20 weight %；Sulfidation
Without artificial sample, work situation is improved, reduces the amount of labour.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
- The on-line control system of vulcanization 1. a kind of hydrogenation plant goes into operation, contains in the on-line control system:(1) hydrogen sulfide on-line checking analysis module, for acquiring and analyzing to catalyst progress presulfurization processing plus hydrogen dress The concentration of hydrogen sulfide in recycle hydrogen set；(2) reaction bed temperature detection module, the temperature of the catalyst bed for detecting and acquiring the hydrogenation plant；(3) vulcanizing agent flow-control module, for controlling the flow for the vulcanizing agent being introduced in the hydrogenation plant；(4) central control module, for compare the concentration of hydrogen sulfide being collected by the hydrogen sulfide on-line checking analysis module with By the temperature for the catalyst bed that the reaction bed temperature detection module is collected into, and according to comparison result to the sulphur Agent flow-control module issues the instruction of vulcanizing agent injection changes in flow rate.
- 2. on-line control system according to claim 1, wherein hydrogen sulfide on-line checking analysis module acquisition is Concentration of hydrogen sulfide in the hydrogen of the circulating hydrogen compressor entrance of the hydrogenation plant.
- 3. on-line control system according to claim 1 or 2, wherein contain DCS unit in the hydrogenation plant, it is described The temperature data of catalyst bed is transferred to the DCS unit, and the center control by reaction bed temperature detection module Molding block and the DCS server carry out data interaction.
- 4. on-line control system described in any one of -3 according to claim 1, wherein the hydrogen sulfide on-line checking analysis Module is to gather combination or the concentration of hydrogen sulfide on-line detector of the sensor of sulfurated hydrogen detection and analysis.
- 5. on-line control system described in any one of -3 according to claim 1, wherein the vulcanizing agent flow-control module In contain vulcanizing agent supply pump, the vulcanizing agent supply pump for realizing in the hydrogenation plant vulcanizing agent injection flow change Change.
- 6. on-line control system described in any one of -5 according to claim 1, wherein the hydrogenation plant is that vapour-liquid adds admittedly Hydrogen production device or liquid-phase hydrogenatin device.
- 7. on-line control system according to claim 1, wherein also contain hydrogen sulfide treatment mould in the on-line control system Block carries out useless for the hydrogen sulfide in recycle hydrogen gas after the hydrogen sulfide on-line checking analysis module is acquired and analyzed Gas disposal.
- A kind of method of vulcanization 8. On-line Control hydrogenation plant goes into operation, this method are containing any one of claim 1-7 institute The hydrogenation plant stated go into operation vulcanization on-line control system device in carry out, this method comprises:(1) by after heating sulfurized oil and vulcanizing agent and recycle hydrogen be concomitantly introduced into the catalyst bed of hydrogenation plant to this The oxidized catalyst contained in catalyst bed carries out vulcanizing treatment；(2) material obtained after the vulcanizing treatment is introduced to gas-liquid separator to separate, obtains gaseous component and liquid phase Component；(3) recycle hydrogen is obtained after being settled the gaseous component, and the recycle hydrogen and new hydrogen are concomitantly introduced into circulation In hydrogen compressor；The liquid phase component is recycled back in step (1) simultaneously；Wherein, in the on-line control system that the hydrogenation plant goes into operation vulcanization, hydrogen sulfide on-line checking analysis module acquisition with And analysis is to the concentration of hydrogen sulfide in the recycle hydrogen of the hydrogenation plant, the detection of reaction bed temperature detection module and acquisition The temperature of the catalyst bed of the hydrogenation plant, central control module is compared to be received by the hydrogen sulfide on-line checking analysis module The temperature of the concentration of hydrogen sulfide collected and the catalyst bed being collected by the reaction bed temperature detection module, and root The instruction of vulcanizing agent injection changes in flow rate is issued to vulcanizing agent flow-control module according to comparison result.
- 9. according to the method described in claim 8, wherein, the vulcanizing agent is inorganic sulphide and/or organic sulfur compound；It is preferred that Ground,The vulcanizing agent is selected from hydrogen sulfide, carbon disulfide, mercaptan, thiophene and derivatives, dialkyl sulfide, dimethyl vulcanization At least one of object and dimethyl sulfide.
- 10. according to the method described in claim 8, wherein, the sulfurized oil is petroleum of the boiling range within the scope of 180~400 DEG C Fraction.
- 11. according to the method described in claim 8, wherein, the sulfurized oil is selected from kerosene, normal two wires distillate, atmosphere 3rd side cut and evaporates Divide at least one of oil, catalytic cracking diesel oil, straight-run diesel oil and coker gas oil；Preferably,The sulfurized oil is straight-run diesel oil and/or kerosene.
- 12. according to the method described in claim 8, wherein, carrier and hydrogenation active metals are contained in the oxidized catalyst Component, and optionally contain auxiliary element；The carrier in aluminium oxide, silica and aluminium oxide-silicon oxide at least one Kind, the hydrogenation active metal component is selected from least one of group VIB and group VIII metallic element；The auxiliary element Selected from least one of phosphorus, fluorine and boron；Preferably,The hydrogenation active metal component is selected from least one of molybdenum, tungsten, cobalt and nickel metallic element.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694696A (en) * | 2019-09-11 | 2020-01-17 | 河北华丰能源科技发展有限公司 | System and method for vulcanizing heating furnace and drying furnace synchronous hydrogenation catalyst |
| CN113707227A (en) * | 2020-05-20 | 2021-11-26 | 中国石油化工股份有限公司 | Carbon-three-liquid phase hydrogenation reactor control method and system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311765A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Startup sulfurization method for trickle bed class-II active center hydrogenation catalyst |
| CN103773454A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst sulfuration method of liquid phase circulating hydrogenation apparatus |
| CN105542852A (en) * | 2015-12-22 | 2016-05-04 | 珠海长炼石化设备有限公司 | Synthetic process method of high-density hydrocarbon |
-
2017
- 2017-10-26 CN CN201711012878.7A patent/CN109701668A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311765A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Startup sulfurization method for trickle bed class-II active center hydrogenation catalyst |
| CN103773454A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Catalyst sulfuration method of liquid phase circulating hydrogenation apparatus |
| CN105542852A (en) * | 2015-12-22 | 2016-05-04 | 珠海长炼石化设备有限公司 | Synthetic process method of high-density hydrocarbon |
Non-Patent Citations (1)
| Title |
|---|
| 盛军波 等: "《苯加氢操作技术》", 31 January 2014, 冶金工业出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110694696A (en) * | 2019-09-11 | 2020-01-17 | 河北华丰能源科技发展有限公司 | System and method for vulcanizing heating furnace and drying furnace synchronous hydrogenation catalyst |
| CN113707227A (en) * | 2020-05-20 | 2021-11-26 | 中国石油化工股份有限公司 | Carbon-three-liquid phase hydrogenation reactor control method and system |
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