CN201433192Y - Device for removing nickel and vanadium from crude oil - Google Patents
Device for removing nickel and vanadium from crude oil Download PDFInfo
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- CN201433192Y CN201433192Y CN2009200771441U CN200920077144U CN201433192Y CN 201433192 Y CN201433192 Y CN 201433192Y CN 2009200771441 U CN2009200771441 U CN 2009200771441U CN 200920077144 U CN200920077144 U CN 200920077144U CN 201433192 Y CN201433192 Y CN 201433192Y
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Abstract
The utility model provides a device comprising a first container used to store crude oil, an oil pump used to circulate the crude oil, a heater used to heat the crude oil, a microwave reactor used tomicrowave treat the crude oil, and a crude oil transfer pipeline used for the circulation of the crude oil by connecting the first container, the oil pump, the heater and the microwave reactor in sequence. According to the utility model, the microwave device is used to treat the crude oil, which is unprecedented in the crude oil processing field and leads to the consequences including a remarkableincrease in the extent to which nickel and vanadium can be removed from the crude oil. Besides, the cost is lower and the operation is easy.
Description
Technical field
The utility model relates to crude oil processing, particularly relates to the device that is used for removing crude oil nickel, vanadium.
Background technology
In recent years along with the reinforcement of domestic and international oil recovery technique, Oilfield using thermal recovery, chemical flooding wet goods technology, and the output of heavy crude increases day by day both at home and abroad, causes that metal content increases in the crude oil.The metal pair Crude Oil Processing that is present in the crude oil is very harmful.Metallic salt can cause catalyst contamination in catalytic cracking process, make light oil yield reduce the quality product variation.In addition, metallic salt can cause that also catalyst deactivation in the hydrogenation process, bed block, defectives such as system pressure increase, thus influence quality product, shorten on-stream time, increase running cost.Metallic salt even also can influence residual oil visbreaking and delay coking process is arranged again.Therefore, before crude oil is carried out atmospheric and vacuum distillation, generally all carry out crude oil upgrading, to remove the metallic salt in the crude oil to greatest extent, to satisfy the basic demand of following process to feed metal content.
Particularly, metallic nickel in the crude oil and vanadium mainly are that the form with the organo-metallic porphyrin compound exists, and it is water insoluble, and therefore conventional electric desalting method is difficult to nickel, vanadium are removed from crude oil, and its harm is very heavy.
Form that nickel, vanadium exist in the based on crude and physics thereof, chemical property have adopted methods such as hydrogenation, solvent extraction, chelating separation to be removed at present.Method from present existing industrialized nickel removal, vanadium also exists a lot of problems.Wherein, the investment of hydrodemetallation (HDM) device is big, and catalyzer be difficult to regeneration, cause spent catalyst to handle.Solvent extraction is to utilize propane, butane equal solvent that bituminous matter in the residual oil and non-asphaltene are separated, promptly by removing the purpose that pitch reaches nickel removal, vanadium, but this kind method also can only remove nickel, vanadium in the high residual oil of asphalt content, and investment is big, the process cost height.Comparatively speaking, if develop nickel, the vanadium sequestrant that consumption is few and sequestering power is strong, the nickel, the vanadium that adopt chelate separation process to remove in the crude oil then can reduce facility investment and process cost.Because complicated component in the crude oil, the structure of nickel, vanadium compound is more stable, thereby can't effectively solve the nickel removal of crude oil, the problem of vanadium with chemical method at present but generally speaking.
Summary of the invention
At the problems referred to above, the purpose of this utility model is to provide a kind of device that is used for removing crude oil nickel, vanadium, and it adopts microwave device that crude oil is handled, thereby significantly improves the decreasing ratio of nickel, vanadium.
For achieving the above object, the utility model provides the method that is used for removing crude oil nickel, vanadium, it is characterized in that, this method comprises the steps:
A) microwave reactor of preparation;
B) get a certain amount of crude oil, and with the temperature of reaction of described heating crude oil to setting;
C) make crude oil enter described microwave reactor;
D) open described microwave reactor, regulate microwave power, described crude oil is stayed for some time in described microwave reactor and be subjected to microwave treatment; And
E) take out described crude oil.
Preferably, described step b) and step c) comprise the steps: the crude oil that is preheated to preheating temperature is put into first container; By oil pump described crude oil is flowed at the pipeline internal recycle from described first container to described microwave reactor, and regulate the rate of discharge of described oil pump; And by electric heater with described heating crude oil to temperature of reaction.
Preferably, this method also comprise the steps: to make described crude oil when circulating through second container, and take out crude oil from described second container.
Preferably, this method also comprise the steps: when described crude oil when circulating, by one or more water circulation systems described crude oil is carried out temperature control.
Preferably, this method also comprise the steps: when described crude oil after described microwave device flows out, make it flow through thermostat.
Preferably, this method comprises the steps: that also described step b) comprises: add metal remover in described crude oil.
The utility model also provides a kind of device that is used for removing crude oil nickel, vanadium, it is characterized in that, this device comprises:
Be used for storing first container of crude oil;
The oil pump that crude oil is circulated and carries;
The well heater that crude oil is heated;
Be used for crude oil is carried out the microwave reactor of microwave treatment; And
Thereby the Crude Oil Transportation pipeline that described first container, described oil pump, described well heater and described microwave reactor are connected in turn crude oil is circulated.
Preferably, this device also comprises: the thermostat that is connected to described microwave reactor.
Preferably, this device also comprises: be connected second container that is used to discharge crude oil that makes in the described Crude Oil Transportation pipeline that crude oil circulates.
Preferably, this device also comprises: be used to control one or more water circulation systems of crude oil temperature, described water circulation system comprises water pump and water heater.
According to the utility model, adopted first and crude oil has been handled at crude oil manufacture field introducing microwave device, the result has significantly improved nickel removal, the vanadium removal effect to crude oil, and compares the low and processing ease of cost with the technology of present existing various nickel removals, vanadium removal.
Description of drawings
Fig. 1 removes the synoptic diagram of the dynamic testing equipment of nickel vanadium in the crude oil according to the utility model preferred embodiment with microwave method.
Embodiment
As shown in Figure 1, the dynamic testing equipment that is used for removing nickel vanadium in the crude oil according to the utility model preferred embodiment mainly comprises first container 1, oil pump 2, well heater 3, microwave reactor 4, thermostat 5 and second container 6.First container 1 and second container 6 are used for storing crude oil.Oil pump 2 (a for example ram pump) and well heater 3 circulate to crude oil respectively and carry and heating.Microwave reactor 4 is used for crude oil is carried out microwave treatment, and this also is a core content of the present utility model, will be described in detail after a while.Thermostat 5 is chucks, can make the crude oil that flows through keep certain temperature, avoids it that cooling takes place and freezes stifled or overheated.
Between each part mentioned above, be connected with the Crude Oil Transportation pipeline, and the Crude Oil Transportation pipeline is provided with control valve.More specifically, first container 1 is connected to oil pump 2 by the Crude Oil Transportation pipeline, is connected to well heater 3, microwave reactor 4 and thermostat 5 successively by corresponding Crude Oil Transportation pipeline again, is connected to second container 6 at last.Microwave reactor 4 is provided with discharge valve 7, is used for discharging the residual crude oil of microwave reactor.Second container 6 is provided with bleeder valve 8, is used to discharge crude oil and sampling.
In addition, be controlled temperature, also be provided with first water circulation system that is used for microwave reactor 4, and second water circulation system that is used for first container 1, second container 6 and thermostat 5.First water circulation system comprises water pump, and second water circulation system comprises water heater and water pump (not shown) respectively, is used for water is heated to certain temperature, and makes it to circulate.
Have again, preferably, near the outlet of microwave reactor 4, be provided with pressure monitoring device,, near the entrance and exit of microwave reactor 4, be provided with device for monitoring temperature, so that the temperature of monitoring crude oil so that monitor effusive former oil pressure.
Below will specifically describe the method that removes the nickel vanadium in the crude oil by above-mentioned dynamic testing equipment.It should be noted that crude oil is by the counter clockwise direction mobile in testing apparatus.
At first, open the pump of first water circulation system that is used for microwave reactor.Open water heater and water pump in second water circulation system again, make water cycle and reach the temperature (being generally 60 ℃) of setting.Then, the crude oil that is preheating to the preheating temperature (for example 50-60 ℃) of setting is joined first container 1, for strengthening the effect of nickel removal, vanadium removal, can in crude oil, add metal remover, for example N2S (diethylamino dithio sodium formiate), N3S (1,2-ethylene amino two (dithio sodium formiate)) or N3PS (two (ethylene) triamino three (dithio sodium formiate)).Follow again, open oil pump 2, regulate the rate of discharge of oil pump 2 by preset flow rate.Subsequently, by regulating the power of well heater 3, crude oil temperature is adjusted to predefined temperature of reaction.After crude oil temperature, flow all reach preset value and stablize, close the valve that enters first container 1 from second container 6, open the bleeder valve 8 of second container.
Secondly, open microwave reactor 4, regulate microwave power, regulate the residence time of crude oil in microwave reactor 4 by the flow of regulating oil pump 2 by regulating electric current.After about 5 minutes after microwave treatment, carry out sampling analysis by the crude oil after 8 pairs of microwave treatment of bleeder valve of second container 6.
Experiment transfers to 0mA with microwave current after finishing, and closes microwave power supply, closes oil pump 2, stops the heating of oil heater and water heater, closes recirculated water, closes general supply.By the discharge valve 7 of microwave reactor 4, emit remaining crude oil in the microwave reactor 4.
Used oil pump 2 is a ram pump in the experiment, and flow is 2.31/h (38ml/min) when each 7 lattice of ram pump front and back, can fill with microwave reaction pipe (volume 105ml/, the 104mm height) this moment.Concrete parameter is as shown in table 1.
Table 1
Crude oil sample after the microwave treatment is carried out the desalting and dewatering experiment, and to measure desalination (nickel, vanadium) rate, concrete steps are as described below.
DPY-1 electric desalting experiment instrument is adopted in this test.Get the 100ml oil sample in test tube, add deionized water 5ml ~ 6ml, add emulsion splitter 50mg/L, behind the concussion 1min, heat 10min down at 85 ℃, shake 1min again, regulating voltage 1800V, constant temperature 20min turns off voltage then, heating 15min takes out the aqueous solution of test tube bottom with needle tubing under 85 ℃.
Take by weighing the 10g oil sample in dry crucible, place on the petroleum products carbon tesidue test device, be heated to and smolder, light ashing with quantitative paper, treat that its afterburnt puts into retort furnace, 550 ℃ of following constant temperature calcinations to eliminating carbon residue, it is wetting to add a small amount of distilled water after the cooling, add the hydrochloric acid of 5mL 6mol/L (1: 1) along wall of cup, crucible is placed on the petroleum products carbon tesidue test device slowly heating for dissolving ash content, remove most of hydrochloric acid (doing), after treating that acid solution is evaporated to 2mL ~ 3mL, it is quantitatively changed in the 50mL volumetric flask, use the distilled water constant volume, shake up.Add developer then, measure the content of nickel, vanadium respectively.
The nickel Determination on content can for example adopt such method: can get 2ml solution to be measured respectively in the 50ml volumetric flask, add one 0.1% p-nitrophenol, the sodium hydroxide that drips 0.02mol/L is to the solution displaing yellow, and the hydrochloric acid soln that drips 0.02mol/L again disappears just to yellow; Add 1.7ml concentration and be 1% NH4F, add the 5mlPH value and be 3.4 KHC8H404-HCl buffered soln, add 3ml concentration again and be 0.02% 5-Br-PADAP, shake up, add 95% ethanol 8.0ml again, be diluted to scale, shake up with deionized water as developer.From adding the developer timing, after 50 minutes, be reference with the blank solution, under 524nm, measure the absorbancy of system, calculate the content of nickel.
The mensuration of content of vanadium can for example adopt such method: get 2ml solution to be measured in the 25ml volumetric flask, add one 0.1% p-nitrophenol, the sodium hydroxide that drips 0.02mol/L is to the solution displaing yellow, the hydrochloric acid soln that drips 0.02mol/L again disappears just to yellow, adding 2mlPH value is 3.4 KHC8H4O4-HCl buffered soln, add 3ml concentration again and be 0.02% 5-Br-PADAP as developer, shake up, place after 50 minutes, add 95% ethanol 8.0ml again, be diluted to scale with deionized water, shake up.From adding the developer timing, after 50 minutes, be reference with the blank solution, under 590nm, measure the absorbancy of system.
Experiment shows that behind the introducing microwave, the effect of crude oil nickel removal and vanadium removal has had significantly to be improved.For defeated (dynamically) crude oil of pipe, when crude oil temperature is 60 ℃, the microwave time is 1 minute, and during microwave power 300W, the nickel removal rate brings up to 7.24% by 0.51% under the no microwave condition; Vanadium removal rate brings up to 22.14% by 14.05% under the no microwave condition.The applicant thinks that this mainly is because microwave has interrupted the reactive force between the molecule, has destroyed the rock steady structure of porphyrin compound, makes metal ion dissociate out from original rock steady structure, thereby crude oil nickel removal, vanadium removal rate are improved.
In addition, can consider effect from microwave power and these two factors of time to the nickel removal vanadium of crude oil.
From experimental result as seen, under certain condition of crude oil temperature and microwave time, along with the increase of microwave power, crude oil nickel removal, vanadium rate increase.For example, be 80 ℃ in the crude oil initial temperature, the microwave time is under the 150W condition at microwave power when being 1min, and the nickel removal rate is 6.34%, and vanadium removal rate is 16.07%; When microwave power increased to 700W, the decreasing ratio of nickel vanadium reached 10.86% and 33.67% respectively.
Table 2: microwave power is to the influence of pipeline oil nickel removal
Table 3: microwave power is to the influence of pipeline oil vanadium removal
Also as can be seen from experimental result, in microwave power and crude oil temperature one timing, the microwave time increases, and is favourable to the nickel removal vanadium.For example, be 700W at microwave power, when crude oil temperature was 80 ℃, when when the microwave time is 1min, the decreasing ratio of nickel was 10.86%, the decreasing ratio of vanadium is 33.67%.When microwave irradiation time was 9min, it was 35.14% that the decreasing ratio of nickel is brought up to, and the decreasing ratio of vanadium reaches 61.02%.
Table 4: the microwave time is to the influence of pipeline oil nickel removal
Table 5: the microwave time is to the influence of pipeline oil vanadium removal
Though abovely describe in detail in conjunction with preferred embodiment right crude oil nickel removal vanadium method and device of the present utility model, but should be appreciated that, be familiar with those of ordinary skill in the art and can on the basis of above disclosure, make the change of various essentially equivalents fully.
For example, what disclose in embodiment of the present utility model is a kind of dynamic testing equipment of simulating actual crude oil processing, but as long as set suitable processing parameter, this dynamic testing equipment can be used for actual explained hereafter fully, therefore will not be confined to " testing apparatus " by the utility model.So-called " dynamic testing equipment " only is a kind of preferred implementation, consideration for short form test and/or production, also can adopt a kind of test/production equipment of static state, that is to say to make crude oil be in flow state, carry out the effect that microwave treatment can reach significant nickel removal, vanadium removal too as long as put it into the microwave reaction device.
Again for example, in embodiment of the present utility model, adopted first container 1 and 6 two containers of second container, but this is not necessary, can only adopts a container to realize charging and discharging yet.In embodiment of the present utility model, adopted first water circulation system and two water control temperature of second water circulation system system, but this also is variable, can be merged into one to them, or employing is more a plurality of, and also can omit under the unallowed situation of condition need not; Perhaps also can adopt other the cold and hot matchmaker outside dewatering.If desired, the thermostat 5 that is adopted in the utility model embodiment also is omissible.
Have again, it should be understood that in the related method of the utility model, can in certain scope, adjust as the case may be such as parameters such as temperature, pressure, microwave power, microwave reaction times.
Owing to there is the possibility of various modification, therefore protection domain of the present utility model should be limited by appended claims, and is not limited to the description in the above-mentioned embodiment.
Claims (10)
1, a kind of device that is used for removing crude oil nickel, vanadium is characterized in that, this device comprises:
Be used for storing first container (1) of crude oil;
The oil pump (2) that crude oil is circulated and carries;
Crude oil is added hot heater (3);
Be used for crude oil is carried out the microwave reactor (4) of microwave treatment; And
With described first container (1), described oil pump (2), described well heater (3) and described microwave reactor (4) thus the Crude Oil Transportation pipeline that is connected in turn crude oil is circulated.
2, device as claimed in claim 1 is characterized in that, this device also comprises: the thermostat (5) that is connected to described microwave reactor (4).
3, device as claimed in claim 1 is characterized in that, this device also comprises: be connected second container (6) that is used to discharge crude oil that makes in the described Crude Oil Transportation pipeline that crude oil circulates.
4, device as claimed in claim 1 is characterized in that, this device also comprises: be used to control one or more water circulation systems of crude oil temperature, described water circulation system comprises water pump and water heater.
5, device as claimed in claim 7 is characterized in that, this device also comprises: be used to control the water circulation system of described microwave reaction actuator temperature, described water circulation system comprises water pump.
6, device as claimed in claim 2 is characterized in that, described thermostat (5) is a chuck.
7, device as claimed in claim 1 is characterized in that, described oil pump (3) is a ram pump.
8, device as claimed in claim 1 is characterized in that, described Crude Oil Transportation pipeline is provided with control valve.
9, device as claimed in claim 3 is characterized in that, described microwave reactor (4) is provided with discharge valve (7), and described second container (6) is provided with bleeder valve (8).
10, device as claimed in claim 1 is characterized in that, is provided with pressure monitoring device near the outlet of described microwave reactor (4), so that the therefrom effusive former oil pressure of monitoring.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009200771441U CN201433192Y (en) | 2009-06-24 | 2009-06-24 | Device for removing nickel and vanadium from crude oil |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009200771441U CN201433192Y (en) | 2009-06-24 | 2009-06-24 | Device for removing nickel and vanadium from crude oil |
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| CN201433192Y true CN201433192Y (en) | 2010-03-31 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102564973A (en) * | 2010-12-17 | 2012-07-11 | 鞍钢股份有限公司 | Method for quickly measuring content of phosphorus, lead and zinc in industrial ferrous dust |
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2009
- 2009-06-24 CN CN2009200771441U patent/CN201433192Y/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102564973A (en) * | 2010-12-17 | 2012-07-11 | 鞍钢股份有限公司 | Method for quickly measuring content of phosphorus, lead and zinc in industrial ferrous dust |
| CN102564973B (en) * | 2010-12-17 | 2013-12-11 | 鞍钢股份有限公司 | Method for quickly measuring content of phosphorus, lead and zinc in industrial ferrous dust |
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Granted publication date: 20100331 |