CN101967392B - Method for denitrification refining of shale oil - Google Patents
Method for denitrification refining of shale oil Download PDFInfo
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- CN101967392B CN101967392B CN 201010522248 CN201010522248A CN101967392B CN 101967392 B CN101967392 B CN 101967392B CN 201010522248 CN201010522248 CN 201010522248 CN 201010522248 A CN201010522248 A CN 201010522248A CN 101967392 B CN101967392 B CN 101967392B
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- shale oil
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- denitrification
- denitrfying agent
- slag
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Abstract
The invention discloses a method for denitrification refining of shale oil, which comprises the following steps: (A) heating the shale oil to 55 to 85 DEG C and mixing the hot shale oil with a denitrfying agent in a static mixer; (B) delivering the mixed shale oil to a settling tank for sedimentation, separating from slag and discharging nitrogen slag from the bottom of the settling tank; and (C) delivering the denitrified shale oil to agglutination separation equipment for further refining. When the process method is used for denitrification refining of the shale oil, the denitrification rate can reach over 80 percent, the shale oleic acid value is increased by less than 100 percent, and the quality of the denitrified shale oil in a subsequent processing process.
Description
Technical field
The present invention relates to a kind of method that shale oil is made with extra care, concrete is the removal methods of shale oil neutral and alkali nitrogen compound.
Background technology
Nitrogenous compound in the shale oil has three classes alkalescence, weakly alkaline and neutral.Basic nitrogen compound is the derivative of pyridine and quinoline system, and the weakly alkaline nitrogen compound is the derivative of azole series, and neutral nitrogen compound then is the derivative of nitrile.These nitrogen compound major parts are useful industrial chemicals, and wherein some part then is considered to affect the reason of shale oil stability.Hydrogenation is desulfurization, denitrogenation, the effective means of the matter of coming unstuck.The hydrofining technology that adopts in the refining of petroleum at present, wherein low-voltage hydrogenation process does not remove substantially to basic nitrogen compound, and high-pressure hydrogenation is then invested greatly, and its use is restricted.But the basic nitrogen compound content in the conventional hydrogenation unit raw material is high, these basic nitrogen compound severe inhibition the hydrodesulfurization reaction of steric hindrance dibenzothiophene, be the maximum inhibition of hydrodesulfurization reaction.Carbazole also can largely hinder hydrodesulfurization reaction, the desulfurization of steric hindrance sulfide and carbazole denitrogenation are vied each other by the hydrogenation approach in catalyst active center, denitrification reaction is slower than desulphurization reaction, it is longer than sulfide that nitride is trapped in time in active centre, therefore can reduce desulfurization rate, and greatly shorten the work-ing life of hydrogenation catalyst.This shows that the basic nitrogen compound that pre-treatment removes in the hydrogenating materials is very necessary.
Chinese patent CN1088606, CN1103106, CN1126749, CN1363644, CN1546611, CN101121900, CN10114403 1 adopt acid denitrfying agent under liquid/liquid two-phase condition petroleum products to be carried out denitrogenation and cooperate high-voltage electric field to separate.Adopt the denitrification process of high-voltage electric field separation method only to be suitable for the very low light lubricating oil base oil of water content, and nitrogenous waste residue separate not exclusively in the oil, affects post-treatment and the use of product, therefore uses to be restricted.
Summary of the invention
The purpose of this invention is to provide and a kind of shale oil is carried out the novel method of denitrification refining, use the method to carry out denitrification refining, the nitrogen slag separates thoroughly, and denitrification effect is good.
In order to realize the foregoing invention purpose, the technical scheme that the application adopts is:
(A) after being heated to 55～85 ℃, mixes in static mixer with denitrfying agent shale oil;
(B) mixed shale oil is sent into sedimentation divides slag in the slurry tank, the nitrogen slag is discharged from the slurry tank bottom;
(C) will send into from the bottom of coarse separation equipment except the shale oil behind the denitrification slag, the air speed of sending into is 0.5h
-1～2.0h
-1Described coarse separation equipment is vertical vessel, and aspect ratio is 2: 1～4: 1, is provided with the wire packing bed in the container; Bed height calculates according to flow and the air speed of device diameters, shale oil, and calculation formula is as follows:
Wherein: H is the thickness (m of unit) of filler; Q is the shale oil hour flow (m of unit
3H
-1); D is coarse separation device diameters (m of unit); V is volume space velocity, the h of unit
-1
The material of above-mentioned wire packing is a kind of in polyvinyl chloride, polypropylene, perfluoroethylene-propylene, tetrafluoroethylene, Inco nickel, Monel, nickel, titanium, titanium alloy or the stainless steel; The weight by volume of wire packing is 80～400Kg/m
3, voidage 85～99m
3/ m
3, specific surface area 150～1000m
2/ m
3
Preferably in slurry tank shale oil is carried out in the settlement separate process, keeping the temperature of shale oil is 55～85 ℃.
Use steaming out coarse separation equipment behind preferred every operation 2000-3000h, with the regeneration wire packing.
The denitrfying agent that uses in the method for the invention is applicant oneself development, this denitrfying agent is applied for patent of invention by the applicant to State Intellectual Property Office, application number: 201010520957.0, patent name: a kind of denitrfying agent that directly from shale oil, removes basic nitrogen compound, this denitrfying agent is by B, L, S, four kinds of one-tenth of water are grouped into, wherein B is phosphoric acid (accounts for denitrfying agent gross weight 40%～80%), L is Lewis acid (accounts for denitrfying agent gross weight 0.1%～10%), S is water-soluble demulsifier (accounts for denitrfying agent gross weight 0.5%), and surplus is water; Lewis acid L is Tai-Ace S 150 Al
2(SO
4)
318H
2O, manganous sulfate MnSO
4H
2O, zinc sulfate ZnSO
47H
2O, copper sulfate CuSO
45H
2O or titanyl sulfate TiOSO
42H
2A kind of among the O; Water-soluble demulsifier S is that initiator is that propylene oxide/oxyethane multi-block polyether, the initiator of straight dihydric alcohol is three block AE type polyethers or three-dimensional netted toxilic acid/olefin copolymers of polyethylene polyamine.Patent application discloses the use proportioning of shale oil and denitrfying agent simultaneously, and namely denitrfying agent mixes in 1: 50～1: 200 ratio of agent-oil ratio with shale oil.
The principle explanation of technical solution of the present invention:
The denitrfying agent of selecting in the inventive method, the B in its prescription can provide H
+With a pair of lone-pair electron complexing salify of basic nitrogen compound, thereby basic nitrogen compound is removed from oil product.L is Lewis acid, can accept a pair of lone-pair electron complexing salify of basic nitrogen compound, and the synergy of B, L has the good basic nitrogen ability of taking off.S has good demulsification, and can improve water-soluble B, L agent in the oil product whipping process with all mixed degree of oil product, thereby improve the nitric efficiency of host;
In full scale plant, improving two useful area that contact is the effective means that improve mass-transfer efficiency.Adopt to consume the way that kinetic energy mixes and stirs, with the two alternate fine drop that break into, increase the two-phase contact area, promote the speed of reaction.But after reaction process was finished, oil/agent two-phase mixed and is difficult to it is separated, although adopt settlement separate equipment, was easy to also occur that oil/agent is carried secretly and emulsion; And the coarse separation equipment of selecting in the application's method is vertical vessel, and countless hairline net fillers are equipped with in inside.When shale oil and nitrogen slag flowed into from the coarse separation device bottom, because capillarity is with capillary different, the nitrogen slag at first formed very thin liquid film on the surface of steel fiber, makes the surface of nitrogen slag be able to great expansion.Oil/nitrogen slag two alternate when mobile frictional force liquid film can be pullled very thin, reaction is that two alternate planar films contact and finish in flowing, for two phase reaction provides maximum contact area, because oily alkali two-phase constantly flows on the silk screen surface, denitrfying agent on the silk screen is also constantly updated, make nitrogen slag liquid remain higher concentration impellent, so coarse separation equipment is the very high reaction mass transfer equipment of a kind of efficient.Because whole reaction process oil/nitrogen slag two-phase remains dispersion, the nitrogen slag hands down the wire direct current at the bottom of the tank after the reaction, and oil/nitrogen slag two-phase can be separated rapidly up hill and dale, has fundamentally avoided emulsification and has carried the appearance of phenomenon secretly;
Eventually the above, denitrfying agent used in the present invention has good denitrification ability, selected coarse separation equipment has again stronger oil/agent separating power, so the application's denitrogenation method has finally produced better denitrification effect.
Beneficial effect of the present invention: adopt above-mentioned processing method that shale oil is carried out denitrification refining, dealkalize nitrogen rate can reach more than 80%; Compare with the acid number of refining front shale oil, the acid number rate increase made from extra care shale oil during not by silk screen foam removal filling batch is a lot, shows that the denitrfying agent of remnants does not settle down in shale oil fully, and denitrfying agent is emulsification in shale oil, and effect of settling is poor.Adopt coarse separation technique effectively to remove and remain in the nitrogen slag made from extra care in the shale oil, refining shale oil acid number is less than 70mgKOH/g, and shale oil acid number increment rate has guaranteed the quality of shale oil following process process after the denitrogenation less than 100%.
Description of drawings
Fig. 1: the flow process of the inventive method and equipment synoptic diagram.
Among the figure: the A-denitrfying agent; The B-shale oil; C-makes with extra care shale oil; D-nitrogen slag; The E-upper grid; The F-wire packing; G-bottom grid; The 1-static mixer; The 2-slurry tank; 3-coarse separation equipment.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is described further, and statement the present invention is not subjected to the restriction of following embodiment.
By shown in Figure 1, the flow process of the inventive method is: shale oil B through the interchanger heat exchange to temperature 55～85? C and denitrfying agent A enter that sedimentation divides slag in the slurry tank 2 in static mixer 1 after the hybrid reaction, and nitrogen slag D discharges from slurry tank 2 bottoms; Removed 95% through the nitrogen slag in the shale oil after the natural subsidence, then enter coarse separation equipment 3, because the density of nitrogen slag is greater than the density of shale oil, so nitrogen slag D makes with extra care rear shale oil C and discharges from coarse separation equipment 3 tops from the discharge of coarse separation equipment 3 bottoms.Coarse separation equipment wherein, comprise a vertical tank, the aspect ratio of tank body is 2: 1～4: 1, the bottom is fixed with bottom grid G in the tank, uniform wire packing F above the screen, be fixed with upper grid E above the wire packing F, wherein the thickness of wire packing bed can calculate according to flow and the shale oil air speed of device diameters, shale oil, and calculation formula is as follows:
Wherein: H is the thickness (m of unit) of filler; Q is the shale oil hour flow (m of unit
3H
-1); D is coarse separation device diameters (m of unit), and V is the volume space velocity (h of unit
-1).
The mensuration of dealkalize nitrogen rate adopts SH/T 0162-92 (confirming in 2000) standard among the following embodiment, and this standard adopts perchloric acid one Glacial acetic acid nonaqueous titrations.Sample is dissolved in an amount of benzene one glacial acetic acid solution, uses perchloric acid one Glacial acetic acid standardized solution titration sample:
The acid number increment rate is defined as follows among the following embodiment:
The height of described acid number increment rate has represented the separating effect of nitrogen slag, and it is qualified that the acid number increment rate is between 0～100%, and the less representative separating effect of acid number increment rate is better.
The used shale oil character of following embodiment sees Table 1:
Table 1 grand celebration shale oil properties
With 2.0g CuSO45H
2O 3.4g water dissolution adds 94g phosphoric acid (85%), adds the three-dimensional netted toxilic acid/olefin copolymer of 0.5g emulsion splitter after mixing again and is re-dubbed denitrfying agent.Get grand celebration shale oil 100g, be to add denitrfying agent at 1: 50 by agent-oil ratio, 65 ℃ of lower stirrings 10 minutes, and keep 65 ℃ of sedimentations after 180 minutes, the nitrogen slag that is deposited in drag is separated with the upper strata shale oil, the upper strata shale oil is keeping passing through silk screen foam removal filling batch (diameter of phi 21mm * height H 42mm) in 65 ℃ of situations, and air speed is 1.0h
-1, the material of wire packing is stainless steel (SUS316L, 00Cr17Ni14Mo2), weight by volume is 120Kg/m
3, specific surface area 210m
2/ m
3, voidage 98.5m
3/ m
3
The basic nitrogen of shale oil drops to 506ppm, dealkalize nitrogen rate 86.6% after refining.The acid number of shale oil is 38.6mgKOH/g before refining, and the acid number of refining rear shale oil is 69.8mgKOH/g, and the acid number increment rate of calculating is 68.8%.Need to prove that this embodiment carries out in the laboratory, the amount of the shale oil that need process is less, so in static mixer, do not mix, but simulated the static mixer mixing in 10 minutes with 65 ℃ of lower stirrings, mixed effect is certainly not as good in static mixer, dealkalize nitrogen rate has reached 86.6% in this case, if mixing can obtain better result in static mixer.Purpose because of the inventive method is to be applied in the production practice in addition, so preferably adopt static mixer to mix during the actual employing of production unit the inventive method.
Embodiment 2 (Comparative Examples)
Feed ratio is identical with embodiment 1 with reaction conditions, difference is not by silk screen foam removal filling batch, after the experimental implementation identical with embodiment 1, the acid number of finding by analysis refining rear shale oil is 166.2mgKOH/g, compare with the acid number of refining front shale oil, the acid number of refining shale oil increase increment rate is 165.2% during not by silk screen foam removal filling batch, shows that remaining denitrfying agent does not settle down in shale oil fully, denitrfying agent is emulsification in shale oil, and effect of settling is poor.
Feed ratio is identical with embodiment 1 with reaction conditions, and difference is that the air speed of control silk screen foam removal filling batch is 0.5h
-1, the basic nitrogen of refining rear shale oil drops to 496ppm, dealkalize nitrogen rate 86.9%.The acid number of shale oil is 38.6mgKOH/g before refining, and the acid number of refining rear shale oil is 63.1mgKOH/g, and the acid number increment rate is 62.1%.Air speed at maintenance silk screen foam removal filling batch is 0.5h
-1Condition under continuous operation after 2000 hours, refining after the acid number of shale oil be 72.2mgKOH/g.Regenerate with 150 steam purging wire packing beds, the wire packing bed continues to come into operation by above-mentioned condition after the regeneration, and the acid number of refining rear shale oil is 65.2mgKOH/g, and the acid number increment rate is 64.2%.
Embodiment 4
Feed ratio is identical with embodiment 1 with reaction conditions, and difference is that the material of wire packing is tetrafluoroethylene, and weight by volume is 80Kg/m
3, specific surface area 155m
2/ m
3, voidage 98.9m
3/ m
3, the basic nitrogen of refining rear shale oil drops to 510ppm, dealkalize nitrogen rate 86.5%.The acid number of shale oil is 38.6mgKOH/g before refining, and the acid number of refining rear shale oil is 66.4mgKOH/g, and the acid number increment rate is 65.4%.
Embodiment 5
Feed ratio is identical with embodiment 1 with reaction conditions, and difference is that the material of wire packing is Inco nickel (Ni 30%Cr 20%Mn1.5%Si1%C more than 0.1% is Fe), and weight by volume is 216Kg/m
3, specific surface area 908m
2/ m
3, voidage 97.3m
3/ m
3, the basic nitrogen of refining rear shale oil drops to 490ppm, dealkalize nitrogen rate 87.0%.The acid number of shale oil is 38.6mgKOH/g before refining, and the acid number of refining rear shale oil is 59.5mgKOH/g, and the acid number increment rate is 58.5%.
Claims (5)
1. one kind is carried out the method for denitrification refining to shale oil, and its concrete step is as follows:
(A) after being heated to 55 ~ 85 ℃, mixes in static mixer with denitrfying agent shale oil; Described denitrfying agent is grouped into by B, L, S, four kinds of one-tenth of water, and wherein B is phosphoric acid, accounts for 40% ~ 80% of denitrfying agent gross weight; L is Lewis acid, accounts for 0.1% ~ 10% of denitrfying agent gross weight; S is water-soluble demulsifier, accounts for 0.5% of denitrfying agent gross weight; Surplus is water; Lewis acid L is Tai-Ace S 150 Al
2(SO
4)
318H
2O, manganous sulfate MnSO
4H
2O, zinc sulfate ZnSO
47H
2O, copper sulfate CuSO
45H
2O or titanyl sulfate TiOSO
42H
2A kind of among the O; Water-soluble demulsifier S is that initiator is that propylene oxide/oxyethane multi-block polyether, the initiator of straight dihydric alcohol is three block AE type polyethers or three-dimensional netted toxilic acid/olefin copolymers of polyethylene polyamine;
(B) mixed shale oil is sent into sedimentation divides slag in the slurry tank, the nitrogen slag is discharged from the slurry tank bottom;
(C) send into coarse separation equipment except the shale oil behind the denitrification slag, the air speed that shale oil is sent into is 0.5h
-1~ 2.0h
-1Described coarse separation equipment is vertical vessel, and aspect ratio is 2:1 ~ 4:1, is provided with the wire packing bed in the container; Bed height calculates according to flow and the air speed of device diameters, shale oil, and calculation formula is as follows:
Wherein: H is the thickness of filler, the m of unit; Q is shale oil hour flow, the m of unit
3H
-1D is the coarse separation device diameters, the m of unit; V is volume space velocity, the h of unit
-1
The material of above-mentioned wire packing is a kind of in polyvinyl chloride, polypropylene, perfluoroethylene-propylene, tetrafluoroethylene, Inco nickel, Monel, nickel, titanium, titanium alloy or the stainless steel; The weight by volume of wire packing is 80 ~ 400Kg/m
3, voidage 85 ~ 99m
3/ m
3, specific surface area 150 ~ 1000m
2/ m
3
2. according to claimed in claim 1 shale oil is carried out the method for denitrification refining, it is characterized in that: in slurry tank shale oil is carried out in the settlement separate process, keeping the temperature of shale oil is 55 ℃ ~ 85 ℃.
3. described shale oil is carried out the method for denitrification refining according to claim 1 or 2, it is characterized in that: the material of wire packing is a kind of in tetrafluoroethylene, Inco nickel or the stainless steel.
4. described shale oil is carried out the method for denitrification refining according to claim 1 or 2, it is characterized in that: behind every operation 2000-3000 h with steaming out coarse separation equipment.
5. according to claimed in claim 3 shale oil is carried out the method for denitrification refining, it is characterized in that: behind every operation 2000-3000h with steaming out coarse separation equipment.
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|---|---|---|---|
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|---|---|---|---|
| CN 201010522248 CN101967392B (en) | 2010-10-28 | 2010-10-28 | Method for denitrification refining of shale oil |
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| CN101967392B true CN101967392B (en) | 2013-01-23 |
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| CN103666537A (en) * | 2013-12-31 | 2014-03-26 | 湖北海育能源科技有限公司 | Coking wax oil complexing denitrification refining method |
| CN108641744B (en) * | 2018-05-11 | 2021-07-06 | 金浦新材料股份有限公司 | Denitrifying agent for denitrifying petroleum products, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4272361A (en) * | 1979-06-27 | 1981-06-09 | Occidental Research Corporation | Method for reducing the nitrogen content of shale oil |
| US4771027A (en) * | 1979-03-19 | 1988-09-13 | Amoco Corporation | Catalyst for the hydrotreating of nitrogen-containing feeds |
| CN1386822A (en) * | 2001-05-18 | 2002-12-25 | 韩剑峰 | Efficient denitrifying agent for removing nitride from fraction oil of petroleum and its denitrifying process |
| CN101121900A (en) * | 2006-08-10 | 2008-02-13 | 中国石化集团武汉石油化工厂 | Denitrogenation hydrogenation combination technique for secondary processing diesel oil |
-
2010
- 2010-10-28 CN CN 201010522248 patent/CN101967392B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4771027A (en) * | 1979-03-19 | 1988-09-13 | Amoco Corporation | Catalyst for the hydrotreating of nitrogen-containing feeds |
| US4272361A (en) * | 1979-06-27 | 1981-06-09 | Occidental Research Corporation | Method for reducing the nitrogen content of shale oil |
| CN1386822A (en) * | 2001-05-18 | 2002-12-25 | 韩剑峰 | Efficient denitrifying agent for removing nitride from fraction oil of petroleum and its denitrifying process |
| CN101121900A (en) * | 2006-08-10 | 2008-02-13 | 中国石化集团武汉石油化工厂 | Denitrogenation hydrogenation combination technique for secondary processing diesel oil |
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