CN105112095B - A kind of method of bio-based fuel oil basic nitrogen compound and phosphatide removing - Google Patents
A kind of method of bio-based fuel oil basic nitrogen compound and phosphatide removing Download PDFInfo
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- CN105112095B CN105112095B CN201510570606.3A CN201510570606A CN105112095B CN 105112095 B CN105112095 B CN 105112095B CN 201510570606 A CN201510570606 A CN 201510570606A CN 105112095 B CN105112095 B CN 105112095B
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Abstract
The present invention discloses a kind of method of the basic nitrogen compound removed in bio-based fuel oil and phosphatide, and this method is realized by two step acid neutralisations and absorption method, wherein the denitrification adsorbent of load acid constituents is to handle adsorbent by two kinds of nitration mixture to be prepared.The first step of the present invention adsorbs denitrogenation, and the denitrification adsorbent of a certain proportion of load acid constituents will be mainly added after bio-based fuel oil point dewater treatment made from catalytic pyrolysis, is warming up to 0.5 2 h of stirring at 50 80 DEG C；Second step acid treatment remove phosphatide, can partial removal basic nitrogen compound, add a certain proportion of acid, 10 30min stirred at 70 90 DEG C.The present invention uses two-step method simple to operate, removing basic nitrogen compound and phosphatide effect good, can preferably solve bio-fuel-oil destabilizing factor, and denitrification adsorbent dosage is few.
Description
Technical field
The present invention relates to a kind of bio-based fuel oil basic nitrogen compound and the method for phosphatide removing, belong to biomass cracking fuel
The technical field of application.
Background technology
Bio-fuel-oil is a kind of renewable and environmentally friendly New-type fuel, and it is using vegetable fat as raw material, passes through catalysis
Liquid fuel made of agent catalytic pyrolysis.Bio-fuel-oil can be widely used for reconciling or directly uses because of it, it is considered to be high-quality
The substitute of petrifaction diesel.
Because it contains more alkene, alkadienes, acid and contains in the bio-fuel-oil that catalytic pyrolysis vegetable fat is prepared
The unstable components such as oxygen, nitrogen-containing compound, because of the effect of oxygen, light and heat in storage process, it is oxidized easily and polymerize and give birth to
Collagen, and the main reason for it darkens and produced precipitation, the nitrogen content in fuel oil is higher, easily corrodes metal
Equipment, NO is formed in combustionX, cause atmosphere pollution.And the presence of phosphatide can influence the quality and oxygen of bio-based fuel oil
Change stability.It is increasingly severe with environmental regulation so that originally less prominent Environmental Factors turn into must pay attention to it is important
Factor.Acid-alkali refining also less, traditional to the report in terms of bio-fuel-oil basic nitrogen compound and phosphatide removing research at present
Though having certain removing effect with adsorption refining, keeping quality is not grown.
The content of the invention
It is an object of the invention to for research deficiency at present herein, there is provided one kind has de- well for bio-fuel-oil
Except basic nitrogen compound and phosphatide effect, and it is refined after its value of bio-fuel-oil storage a period of time can keep constant.The present invention
A kind of method for removing basic nitrogen compound and phosphatide is provided, its is simple and easy to do, and pollution is few, both economical, solves bio-fuel-oil
Oxidation stability is poor, discoloration is fast.
The invention mainly includes steps：
Above-mentioned purpose of the present invention is realized by two-step pretreatment：
(1) preparation of the denitrification adsorbent of acid constituents is loaded：With any one in porous material activated carbon, carclazyte, diatomite
Kind or two kinds of mixing are used as base material；Base material pre-processes, that is, takes a certain amount of base material to add concentrated hydrochloric acid immersion treatment one as in beaker
The section time, wash to neutrality, 12h is dried at 120 DEG C.Acid load, that is, prepare 10%-30% sulfuric acid, phosphoric acid, nitric acid, grass
Any one or more in acid solution, add organic acid：Any one in benzoic acid, p-methyl benzenesulfonic acid, ethanedioic acid, its is pre-
Base material immersion 6h after processing, 12h is dried at 105 DEG C, produces the denitrification adsorbent of load acid constituents.
(2) by bio-fuel-oil dewater treatment made from catalytic pyrolysis, the oil after dehydration is taken, adds oil weight 1%-2% place
Adsorbent after reason, 1h is stirred at 65 DEG C -80 DEG C, filter.
(3) take the good oil of above-mentioned filtering, 15min stirred at 90 DEG C, at the same be slowly added to 2mL 70% phosphoric acid, hydrochloric acid,
Any one in sulfuric acid or two kinds of mixing, stand 5min.
(4) water of oily weight 4% is added, 5min is stirred at 75 DEG C, water is removed in layering, and distilled water or salt solution are cleaned to water layer
PH=7, vacuum decompression distillation dehydration.
The advantage of the present invention compared with prior art has：
(1) denitrification adsorbent of load acid constituents of the invention is to the basic nitrogen compound and phosphatide that contain in bio-based fuel oil
Removal effect is good, the defects of can effectively solve the problem that bio-based fuel oil stability difference made from grease catalytic pyrolysis, can effectively improve
The quality and stability in storage of bio-based fuel oil, and the use range of bio-based fuel oil can be expanded.
(2) present invention process flow is simple, easy to operate, and cost of manufacture is cheap, preparation method is simple, safety and environmental protection.It is logical
The fuel crossed after processing is used to start function to reduce smoke intensity and nitride in exhaust emissions.
(3) the bio-based fuel oil that the present invention sour neutralisation of combination and absorption method two-step pretreatment handle to obtain can be with arbitrary proportion
Blending can alleviate the crisis of fossil energy to a certain extent in petrifaction diesel, and sustainability harmonious society can be promoted to send out
Exhibition.
Embodiment
The present invention is further explained with reference to specific example, but instantiation does not do any restriction to the present invention.
Example 1
This example prepares bio-fuel-oil with soybean oil catalytic pyrolysis, and it is 20% sulfuric acid that it, which loads the denitrification adsorbent of acid constituents,
Activated carbon is soaked with p-methyl benzenesulfonic acid, second step is handled using 70% phosphoric acid.
By the denitrification adsorbent of above-mentioned load acid constituents and obtained soybean oil bio-fuel-oil with 1:100 mix, at 65 DEG C
1h is stirred, is filtered to remove adsorbent.Oil sample after filtering is taken, 70% phosphoric acid solution is added, 15min is stirred at 90 DEG C, add oil
4% water is weighed, after stirring a period of time at 75 DEG C, bio-fuel-oil after must handling.；Entered in separatory funnel, after stratification,
Lower floor's liquid is removed, retains upper strata edible vegetable oil, then is washed 3 times with deionized water, to water layer pH=7, last vacuum decompression distillation is de-
Water.Catalytic pyrolysis alkalescence nitrogen oxides is detected with perchloric acid-glacial acetic acid non-aqueous titration SH/T0162-92, with grain and oil detection phosphorus
The measure GB/T5537-2008 content of phospholipid of fat content.
Basic nitrogen compound changes bio-fuel-oil with phosphatide before and after the processing in the example 1 of table 1
| Project | Test method | Before processing bio-fuel-oil | Bio-fuel-oil after processing | Bio-fuel-oil after one week |
| Alkaline nitrogen oxides (ppm) | SH/T0162-92 | 167.24 | 5.23 | 5.46 |
| Phosphatide (mg/g) | GB/T5537-2008 | 19.78 | 0.43 | 0.45 |
As it can be seen from table 1 the basic nitrogen compound and phosphatide of bio-fuel-oil prepared by this example soybean oil catalytic pyrolysis
Comparision contents are high, and it is preserved and had a significant impact, it is necessary to first be removed.By two-step pretreatment, it can be seen that basic nitrogen compound
Significantly decline with the content of phosphatide, alkali nitrogen is by 167.24ppm to 5.23ppm, and removal efficiency is up to 96.8%, and phosphatide is by 19.78mg/
G drops to 0.43mg/g, and removal efficiency is up to 97.8%, it is possible thereby to illustrate two-step pretreatment to having obvious denitrogenation and dephosphorization fat to imitate
Fruit.The changes of contents of one week its alkali nitrogen of placement and phosphatide is little, illustrates that two-step pretreatment can effectively improve the oxidation peace of bio-fuel-oil
It is qualitative.
Example 2
This example prepares bio-fuel-oil with wilson dogwood oil catalytic pyrolysis, and it is 15% sulphur that it, which loads the denitrification adsorbent of acid constituents,
Acid and p-methyl benzenesulfonic acid immersion activated carbon, second step are handled using 70% phosphoric acid.
By the denitrification adsorbent of above-mentioned load acid constituents and obtained wilson dogwood bio-fuel-oil with 2:100 mix, at 65 DEG C
1h is stirred, is filtered to remove adsorbent.Oil sample after filtering is taken, 70% phosphoric acid solution is added, 15min is stirred at 90 DEG C, add oil
4% water is weighed, after stirring a period of time at 75 DEG C, bio-fuel-oil after must handling.；Entered in separatory funnel, after stratification,
Lower floor's liquid is removed, retains upper strata edible vegetable oil, then is washed 3 times with deionized water, to water layer pH=7, last vacuum decompression distillation is de-
Water.Catalytic pyrolysis alkalescence nitrogen oxides is detected with perchloric acid-glacial acetic acid non-aqueous titration SH/T0162-92, with grain and oil detection phosphorus
The measure GB/T5537-2008 content of phospholipid of fat content.
Basic nitrogen compound changes bio-fuel-oil with phosphatide before and after the processing in the example 2 of table 2
| Project | Test method | Before processing bio-fuel-oil | Bio-fuel-oil after processing | Bio-fuel-oil after one week |
| Alkaline nitrogen oxides (ppm) | SH/T0162-92 | 136.24 | 4.23 | 4.37 |
| Phosphatide (mg/g) | GB/T5537-2008 | 22.87 | 0.26 | 0.31 |
From table 2 it can be seen that the basic nitrogen compound and phosphatide of bio-fuel-oil prepared by this example wilson dogwood oil catalytic pyrolysis
Comparision contents it is high, all have a significant impact post-processing and preserving, it is necessary to first be removed.By two-step pretreatment, can see
The content for going out basic nitrogen compound and phosphatide significantly declines, and alkali nitrogen is by 136.24ppm to 4.23ppm, and removal efficiency is up to 96.9%, phosphorus
Fat drops to 0.26mg/g by 22.87mg/g, and removal efficiency is up to 98.9%, it is possible thereby to illustrate two-step pretreatment to there is obvious denitrogenation
With dephosphorization fat effect.It is little to place the changes of contents of one week its alkali nitrogen and phosphatide, illustrates that two-step pretreatment can effectively improve biological combustion
The oxidation stability of oil.
Example 3
This example prepares bio-fuel-oil with hogwash fat catalytic pyrolysis, and it is 25% sulfuric acid that it, which loads the denitrification adsorbent of acid constituents,
Activated carbon is soaked with p-methyl benzenesulfonic acid, second step is handled using 70% phosphoric acid.
By the denitrification adsorbent of above-mentioned load acid constituents and obtained bio-fuel-oil with 2:100 are mixed, and 1h is stirred at 75 DEG C,
It is filtered to remove adsorbent.Oil sample after filtering is taken, 70% phosphoric acid solution is added, stirs 15min at 90 DEG C, add oily weight 4%
Water, after stirring a period of time at 75 DEG C, bio-fuel-oil after must handling.；Entered in separatory funnel, after stratification, under removing
Layer liquid, retain upper strata edible vegetable oil, then washed 2-3 times with deionized water, it is de- in neutrality, last vacuum decompression distillation to water layer pH
Water.Catalytic pyrolysis alkalescence nitrogen oxides is detected with perchloric acid-glacial acetic acid non-aqueous titration SH/T0162-92, with grain and oil detection phosphorus
The measure GB/T5537-2008 content of phospholipid of fat content.
Basic nitrogen compound changes bio-fuel-oil with phosphatide before and after the processing in the example 3 of table 3
| Project | Test method | Before processing bio-fuel-oil | Bio-fuel-oil after processing | Bio-fuel-oil after one week |
| Alkaline nitrogen oxides (ppm) | SH/T0162-92 | 189.52 | 7.34 | 7.48 |
| Phosphatide (mg/g) | GB/T5537-2008 | 26.59 | 0.83 | 0.93 |
From table 3 it can be seen that the basic nitrogen compound and phosphatide of bio-fuel-oil prepared by this example hogwash fat catalytic pyrolysis
Comparision contents are high, and it is preserved and had a significant impact, it is necessary to first be removed.By two-step pretreatment, it can be seen that basic nitrogen compound
Significantly decline with the content of phosphatide, alkali nitrogen is by 189.52ppm to 7.34ppm, and removal efficiency is up to 96.1%, and phosphatide is by 26.59mg/
G drops to 0.83mg/g, and removal efficiency is up to 96.8%, it is possible thereby to illustrate two-step pretreatment to having obvious denitrogenation and dephosphorization fat to imitate
Fruit.The changes of contents of one week its alkali nitrogen of placement and phosphatide is little, illustrates that two-step pretreatment can effectively improve the oxidation peace of bio-fuel-oil
It is qualitative.
Claims (2)
1. a kind of method of basic nitrogen compound removed in bio-based fuel oil and phosphatide, is neutralized by acid and two steps of absorption reach mesh
's；Specifically comprise the following steps：
(1) by bio-based fuel oil elder generation dewater treatment, the denitrification adsorbent that oil weighs 1%-2% is added, 1h is stirred at 65-80 DEG C,
Filtering；
(2) oil after filtering is stirred into 15min at 90 DEG C, while be slowly added in 2mL 70% phosphoric acid, hydrochloric acid, sulfuric acid
The mixing of any one or two kinds, stands 5min；
(3) water of oily weight 4% is added, 5min is stirred at 75 DEG C, layering is removed water, cleaned with distilled water or salt solution to water layer pH=7,
Vacuum decompression distillation dehydration；
Adsorbent in the step (1) is prepared according to the following steps：With any one in porous material activated carbon, carclazyte, diatomite
Kind or two kinds of mixing are used as base material；Base material pre-processes, that is, takes a certain amount of base material to be placed in beaker, adds concentrated hydrochloric acid immersion treatment one
The section time, wash to neutrality, 12h is dried at 120 DEG C；Acid load, that is, prepare 10%-30% sulfuric acid, phosphoric acid, nitric acid, grass
Any one or more in acid solution, add organic acid：Any one in benzoic acid, p-methyl benzenesulfonic acid, ethanedioic acid, it will pass through
Pretreated base material, which is put into mixed acid, soaks 6h, and 12h is dried at 105 DEG C, produces the denitrification adsorbent of load acid constituents.
2. a kind of denitrification adsorbent for loading acid constituents, it is characterised in that the adsorbent is prepared according to the following steps：With porous material
Any one in activated carbon, carclazyte, diatomite or two kinds of mixing are used as base material；Base material pre-processes, that is, takes a certain amount of base material to be placed in
In beaker, add concentrated hydrochloric acid immersion treatment for a period of time, wash to neutrality, 12h is dried at 120 DEG C；Acid load, that is, prepare
Any one or more in 10%-30% sulfuric acid, phosphoric acid, nitric acid, oxalic acid solution, add organic acid：Benzoic acid, to methylbenzene
Any one in sulfonic acid, ethanedioic acid, it will be put into by pretreated base material in mixed acid and soak 6h, dried at 105 DEG C
12h, produce the denitrification adsorbent of load acid constituents.
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| CN102008938A (en) * | 2010-11-15 | 2011-04-13 | 中国石油化工股份有限公司 | Naphtha denitrification adsorbent and preparation method thereof |
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