CN103102967B

CN103102967B - Wax oil hydrotreating method for diesel oil by-production

Info

Publication number: CN103102967B
Application number: CN201110353769.8A
Authority: CN
Inventors: 刘涛; 单广波; 彭冲; 刘继华; 黄新露; 董立廷
Original assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: China Petroleum and Chemical Corp; Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 2011-11-10
Filing date: 2011-11-10
Publication date: 2015-02-18
Anticipated expiration: 2031-11-10
Also published as: CN103102967A

Abstract

The present invention relates to a wax oil hydrotreating method for diesel oil by-production. According to the method, under a hydrogenation condition, a biological oil and circulation hydrogen are mixed, and pass through a first stage hydrogenation reaction zone, the stream generated from hydrogenation is separated to obtain hydrogen-rich gas, the hydrogen-rich gas is recycled, the separated liquid and the wax oil raw material oil are mixed and enter a second stage wax oil hydrotreating reaction zone, the sub-hydrogen gas separated from the oil generated through second stage hydrogenation is recycled, and the separated liquid product is subjected to fractionation to obtain naphtha, diesel oil and hydrogenation wax oil, wherein hydrogenation activity components of the hydrogenation catalyst used at the first stage are one or a plurality of materials selected from sulfurization state W, Mo, Ni and Co under a reaction state. Compared to the method in the prior art, the wax oil hydrotreating method of the present invention has the following characteristics that: the high quality diesel oil can be by-produced on the wax oil hydrotreating device, activity stability of the catalyst is good, and the device can stably operate for a long period.

Description

A kind of wax oil hydrogenation treatment process of by-product diesel oil

Technical field

The present invention relates to a kind of method of hydrotreating, particularly a kind of can the wax oil hydrogenation treatment process of by-product diesel oil.

Background technology

The energy in current global range is mainly derived from fossil energy, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality trend aggravation, and world economy sustainable development, environmental regulation increasingly stringent need to produce a large amount of light clean fuel, these increase new oil substitutes while all requiring to improve existing oil Refining Technologies, produce satisfactory product with minimum cost.Catalytic cracking is one of important means of light materialization of heavy oil, but along with in poor quality and the heaviness of catalyzed cracking processing raw material, its operational condition is more and more harsher, light-end products yield and product property are deteriorated, and hydrotreating of FCC feedstock technology not only can remove the content of desulfuration, nitrogen, metal impurities, also can improve the cracking performance of charging, reduce FCC operating severity; Improve product slates, improve object product selectivity; Reduce dry gas and coke yield, improve the economy of FCC apparatus; Reduce object product sulphur content; SOx and NOx content etc. in minimizing regenerated flue gas.

Bio-oil, as renewable resources, obtains the extensive attention in the world, and each research unit and enterprise are all making great efforts to carry out its research as clean energy.The method production biofuel (being generally fatty acid methyl ester) utilizing transesterify has been proven technique, but because fatty acid methyl ester oxygen level is high, although many countries and regions have put into effect the standard of biofuel successively, and are not suitable for all oil engines.Bio-oil produces automotive fuel by the method for hydrogenation, and all remove by oxygen or partly remove the product produced and meet automotive fuel standard, this method directly can meet the requirement of existing market.

Existing animal-plant oil hydrogenation method produces the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose vegetables oil hydroconversion process, adopt coker naphtha, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), the petroleum hydrocarbon cuts such as wax oil cut and bio-oil are mixed into hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses the diesel oil blending component producing diesel oil distillate scope containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation.EP1741767 and EP1741768 discloses a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil first through hydrotreatment, then by isomerization catalyst bed layer, obtain low freezing point diesel fuel component, but owing to generating water in hydroprocessing processes, cause very adverse influence to isomerization catalyst, device can not long-period stable operation.US20110155636 discloses a kind of hydroprocessing process containing biomass material, employs Fe system, catalyzer that Cu system, chromium system metal steam are changed.

For wax oil hydrogenation treatment technology, mainly for the feature of wax oil raw material, select the catalyst loading technology of grating and the operational condition of optimization, for catalytic cracking unit provides the raw material after hydrogenation.CN200910204292.X discloses a kind of wax oil liquid phase circulation method of hydrotreating, CN101376840 and CN101376841 discloses a kind of heavy distillate oil hydrotreating method, CN10108913 discloses a kind of hydroprocessing process, US3983029 and US6793804 discloses wax oil hydrogenation treatment technology and catalyzer, these above-mentioned method by-products obtain the density 0845 ~ 0.870g/cm of diesel oil distillate ³cetane value 40 ~ 50, sulphur content 51 ~ 1000 μ g/g, directly can not meet the requirement of the Europe IV standard or higher standard, and having have passed through a hydrogenation technique due to this diesel oil distillate, the difficulty of its further hydrogenating desulfurization is also very large, therefore in some techniques, wax oil hydrogenation process wax oil not as the blend component of diesel product, and still goes catalytic cracking.

CN101348732 discloses a kind of heavy distillate oil hydrotreating method, mainly bio-oil is directly mixed refining to VGO, the working method of the character diesel oil that then improved by fractionation.But the H generated in the course of processing of the method ₂o has very adverse influence to wax oil hydrogenation catalyzer, and CO and CO that bio-oil hydrogenation reaction generates ₂the performance of hydrogenation catalyst is had a negative impact, simultaneous methanation reaction will increase considerably temperature rise, even reach uncontrollable degree, the methane of final generation is difficult to discharge system, thus greatly reduce the hydrogen dividing potential drop of reactive system, or discharge methane by the method for discharge, so just increase considerably the hydrogen consumption of device.

Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is that bed carbon distribution causes shorten running period, need more catalyst changeout of often stopping work, particularly independent with bio-oil be raw material or bio-oil blending ratio higher time, the running period of hydrogenation catalyst is more subject to obvious impact.And for mixing the hydrogenation unit of refining bio-oil, the H that reaction process generates ₂o, CO and CO ₂and CH ₄very adverse influence can be produced Deng to existing hydrogenation catalyst system.

In prior art, bio-oil hydrogenation produces the method for automotive fuel, petroleum fractions (gasoline, diesel oil, wax oil or the residual oil) hybrid process of general needs and larger proportion, or directly by hydrofining-catalyst for hydro-upgrading bed, the H that reaction process generates ₂o, CO and CO ₂and CH ₄very adverse influence can be produced Deng to existing hydrogenation catalyst system, affect the life-span of plant running cycle or catalyzer.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first paragraph hydrofining (the bio-oil raw material DNA vaccine that the hydrogenation catalyst of grating and control are suitable for), second segment first paragraph hydrogenated oil and the process of wax oil distillate mixed hydrogenation, can directly with by-product fine-quality diesel oil while production hydrogenation wax oil, have wax oil hydrogenation process catalysts influence little, the advantages such as the plant running cycle is long.Control the DNA vaccine be suitable in bio-oil hydrogenation process, be conducive to the stability of bio-oil hydrogenation process and the stability of wax oil hydrogenation treating processes simultaneously.

Summary of the invention

For the deficiencies in the prior art, the invention provides a kind of method of hydrotreating being stock oil by-product diesel oil with bio-oil and wax oil distillate, first bio-oil and recycle hydrogen are by loading hydrogenation catalyst first paragraph reaction zone, then liquid and wax oil distillate are mixed into the second segment reaction zone of loading wax oil hydrogenation process catalyzer, can direct production fine-quality diesel oil and hydrogenation wax oil, have hydrogenation process to stablize, running period is long, affects the features such as little to wax oil hydrogenation processing reaction district.

The wax oil hydrogenation treatment process of a kind of by-product of the present invention diesel oil comprises following content:

(a) with wax oil cut for stock oil, with one or more in bio-oil for auxiliary material;

B () is under Hydroprocessing conditions, bio-oil and recycle hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first bio-oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is one or more in W, Mo, Ni and Co of sulphided state;

C () first paragraph reaction zone hydrogenation effluent is separated the gas circulation obtained and uses, liquid phase generates oily entering with wax oil feedstock and uses the second segment reaction zone of wax oil hydrogenation process catalyzer to carry out hydrotreatment reaction;

D the gas phase of () second segment reaction zone resultant stream gas-liquid separation recycles, liquid phase fractionation in separation column of second segment reaction zone liquid phase resultant stream gas-liquid separation obtains petroleum naphtha, diesel oil and hydrogenation wax oil.

In the inventive method step (a), the bio-oil used can comprise vegetables oil and/or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and rice bran wet goods, and animal grease comprises one or more in butter, lard, sheep oil and fish oil etc.Wax oil distillate one or more mixing oils mainly in VGO, CGO or DAO.In the inventive method, first paragraph reaction zone liquid phase generates oil and accounts for 5% ~ 40% of second segment reaction zone liquid phase feeding weight, is preferably 10% ~ 30%.

In the inventive method step (b), the Hydroprocessing conditions of first paragraph reaction zone is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h ^-1~ 8.0h ^-1, average reaction temperature 180 DEG C ~ 425 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 1.0h ^-1~ 4.0h ^-1, average reaction temperature 200 DEG C ~ 400 DEG C.The DNA vaccine of first paragraph reaction zone bio-oil raw material controls to be 40% ~ 95%, is preferably 60% ~ 90%.

In the inventive method step (b), beds generally can arrange 2 ~ 5, in the beds that first reaction mass passes through, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%, the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone, preferably 20% ~ 70%, best 30% ~ 60%.The hydrogenation active component content of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer, preferably increases by 5 ~ 20 percentage points.Beds generally can arrange 2 ~ 5.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent, as P, Si, B, Ti, Zr etc. simultaneously.Can commercial catalyst be adopted, also can by the existing method preparation in this area.The business hydrogenation catalyst that first reaction zone uses mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, the hydrogenation catalysts such as ICR179, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.

In the inventive method step (b), reaction system hydrogen sulfide in gas phase concentration controls higher than 0.005v%, preferred 0.01v% ~ 2.0v%, to maintain the sulfided state of catalyst stabilization, keeps catalytic activity.Specifically can be realized by the method for adding S-contained substance in reaction mass, also the circulation gas containing hydrogen sulfide in step (c) can be circulated in step (b) and use.Containing water in the hydrogenation effluent of first paragraph reaction zone, suitable method can be adopted to remove, as cooled rear separation removal.First paragraph reaction zone hydrogenation effluent is separated the gas phase obtained and can uses at first paragraph reaction zone internal recycle, also can as the hydrogen make-up of second segment reaction zone.The gas phase of second segment reaction zone resultant stream gas-liquid separation recycles in second reaction zone, also can be circulated to the first reaction zone on a small quantity.

In the inventive method step (c), the Hydroprocessing conditions of second segment reaction zone is generally reaction pressure 4.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h ^-1~ 5.0h ^-1, average reaction temperature 280 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 5.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 400:1 ~ 2500:1, volume space velocity 0.1h ^-1~ 4.0h ^-1, average reaction temperature 300 DEG C ~ 460 DEG C.First paragraph reaction zone hydrogenation effluent does not need cooling to carry out gas-liquid separation, and the water that reaction generates enters in gas phase.The working pressure of second segment reaction zone can be identical with first paragraph, also can be different.

In the inventive method step (c), the hydrotreating catalyst of second segment reaction zone can use the hydrogenation catalyst of this area routine, specifically can comprise protective material, Hydrodemetalation catalyst and Hydrobon catalyst etc.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent, as P, Si, B, Ti, Zr etc. simultaneously.Can commercial catalyst be adopted, also can by the existing method preparation in this area.The business hydrogenation protecting agent that second segment reaction zone uses mainly contains, the RF series protective material that the ICR series protective material of CHEVRON company exploitation and catalyst for demetalation, Uop Inc. develop, the RG series protective material of RIPP exploitation, the serial protective material of KG of AKZO company exploitation and FZC series protective material and the catalyst for demetalation etc. of FRIPP exploitation.The business hydrotreating catalyst that first paragraph reaction zone uses mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, hydrogenation catalyst such as ICR 179 grade, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.The high metal content hydrogenation catalyst that the main hydrotreating catalyst that second segment reaction zone uses can use with first paragraph reaction zone is same catalyzer, may not be same catalyzer.

In the inventive method, first paragraph and second segment reaction zone hydrogenation active component are the catalyzer of oxidation state, carry out conventional sulfidizing before the use, make hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.Wax oil feedstock can be the reduced pressure distillate that crude oil underpressure distillation obtains.

Accompanying drawing explanation

Fig. 1 is the wax oil hydrogenation treatment process principle flow chart of a kind of by-product diesel oil of the present invention.

Fig. 2 is the another one principle flow chart of the wax oil hydrogenation treatment process of a kind of by-product diesel oil of the present invention.

Embodiment

Method of the present invention is specific as follows: the mixing oil of one or more in bio-oil and recycle hydrogen under Hydroprocessing conditions by comprising the first paragraph hydroconversion reaction zone of at least two kinds of hydrogenation catalysts, the hydrogenated oil obtained be separated in high-pressure separator (abbreviation high score) gas obtained mix with the gas phase of second segment reaction zone reaction product carry out dewatering and depriving hydrogen sulphide process Posterior circle use, the liquid distillate obtained and wax oil distillate and recycle hydrogen are mixed into the second segment reaction zone comprising serial wax oil hydrogenation process catalyzer, obtain hydrotreatment logistics to be separated in high-pressure separator (abbreviation high score) gas obtained and to recycle at second segment, the liquid fractionation obtained obtains following products: gas, petroleum naphtha, fine-quality diesel oil and hydrogenation wax oil.The bio-oil that embodiment uses is commercially available prod, uses front filtering solid impurity.

Particular case of the present invention is further illustrated below by embodiment.The first paragraph reaction zone of embodiment 1 and embodiment 2 uses the component loops hydrogen (as Fig. 2 flow process) of second segment reaction zone, and embodiment 3 first paragraph reaction zone uses vulcanizing agent to maintain hydrogen sulfide content (as Fig. 1 flow process).

The main composition of table 1 catalyzer and character.

Catalyzer

Catalyzer 1

Catalyzer 2

Catalyzer 3

Protective material

Hydrodemetalation catalyst

Hydrotreating catalyst

Catalyzer forms

MoO ₃，wt%

5.4

10.8

23.9

7.0

12.5

24.9

NiO，wt%

1.8

4.7

2.0

3.0

4.9

CoO，wt%

3.3

Alumina supporter, wt%

Surplus

The main character of catalyzer

Specific surface, m ²/g

>130

>160

>100

>110

>130

Pore volume, ml/g

>0.30

>0.60

>0.50

>0.30

Table 2 stock oil main character.

Stock oil	Wax oil raw material 1	Wax oil raw material 2	Soybean oil	Oleum Gossypii semen
					S，wt%	1.50	3.20	<0.001	<0.001
N，wt%	0.110	0.26	<0.002	<0.002
					Aromatic hydrocarbons, wt%	53.4	69.7	<0.05	<0.05
V+Ni，μg/g	1.1	4.9	<0.001	<0.001

Table 3 embodiment and reference example processing condition and test-results.

First paragraph reaction zone processing condition	Embodiment 1	Reference example	Embodiment 2	Embodiment 3
					Catalyzer	Catalyzer 1/ catalyzer 3		Catalyzer 1/ catalyzer 2/ catalyzer 3	Catalyzer 1/ catalyzer 2
Catalyst volume ratio	20:80		20:30:50	40:60
					Stock oil	Soybean oil		Soybean oil	Oleum Gossypii semen
Reaction pressure, MPa	8.0		12.0	6.0
					Entrance hydrogen to oil volume ratio	1000:1		1000:1	1000:1
Cumulative volume air speed, h ^-1	3.3		1.5	5.0
					Average reaction temperature, DEG C	325		340	330
Vulcanizing agent	DMDS		DMDS	DMDS
					Hydrogen sulfide content, v%	0.10		0.10	0.10
First paragraph reaction zone DNA vaccine, %	80		90	82
					Second segment reaction zone processing condition
Catalyzer	Protective material/hydrotreating catalyst	Protective material/hydrotreating catalyst	Protective material/hydrotreating catalyst	Protective material/metal remover/hydrotreating catalyst
					Catalyst volume ratio	9:91	9:91	10:90	11:19:70
Stock oil, weight	85% wax oil 1+15% first paragraph generates oil	85% wax oil 1+15% soybean oil	90% wax oil 2+10% first paragraph generates oil	890% wax oil 1+20% first paragraph generates oil
					Reaction pressure, MPa	8.0	8.0	12.0	6.0
Entrance hydrogen to oil volume ratio	1000:1	1000	800:1	500:1
					Volume space velocity, h ^-1	1.4	1.0	2.5	1.0
Average reaction temperature, DEG C	390	390	385	370
					Operate CO+CO in 200 hours Posterior circle gas ₂+CH ₄, volume %	3.9	8.7	3.4	2.1
Hydrogenated diesel oil product
					Yield, wt%	26.9	25.7	22.4	29.1
Density, g/cm ³	0.830	0.831	0.835	0.829
					Sulphur content, μ g/g	78	80	78	230
Cetane value	71	65	62	79
					Hydrogenation wax oil product
Sulphur content, μ g/g	1000	1040	1550	1900
					Nitrogen content, μ g/g	550	570	660	1200
Aromatic hydrocarbons, volume %	24.8	25.6	28.9	35.5
					Metal (Ni+V), μ g/g	<0.5	<0.5	<0.5	<0.5

As can be seen from embodiment, by the wax oil hydrogenation treatment process of this technology can under the prerequisite of producing hydrogenation wax oil by-product fine-quality diesel oil product, and can long-period stable operation be realized.The inventive method has promoter action to wax oil hydrogenation processing reaction simultaneously, and when close desulfurization degree, the inventive method can operate at a high space velocity, and namely the treatment capacity of device can significantly improve.

Claims

1. a wax oil hydrogenation treatment process for by-product diesel oil, is characterized in that comprising following content:

B () is under Hydroprocessing conditions, bio-oil and recycle hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first bio-oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is the W of sulphided state, Mo, one or more in Ni and Co, in the beds that first reaction mass passes through, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%, the hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer,

2. method according to claim 1, is characterized in that: in step (a), and the bio-oil of use comprises vegetables oil and/or animal grease.

3. method according to claim 1, is characterized in that: in step (b), and the reaction pressure of first paragraph reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h ^-1~ 8.0h ^-1, average reaction temperature 180 DEG C ~ 425 DEG C.

4. in accordance with the method for claim 1, it is characterized in that: in step (b), the hydrogen to oil volume ratio 300:1 ~ 2500:1 of first paragraph reaction zone, volume space velocity 1.0h ^-1~ 4.0h ^-1, average reaction temperature 200 DEG C ~ 400 DEG C.

5. the method according to claim 1 or 3, is characterized in that: in step (b), and first paragraph reaction zone beds arranges 2 ~ 5, and the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone.

6. method according to claim 5, is characterized in that: in step (b) first paragraph reaction zone, and the hydrogenation catalyst that first reaction mass passes through accounts for 20% ~ 70% of all hydrogenation catalyst volumes in first paragraph reaction zone; The hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 5 ~ 20 percentage points in oxide weight than adjacent upstream catalyzer.

7. method according to claim 1, is characterized in that: in step (c), and the reaction pressure of second segment reaction zone is 4.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 3000:1, and volume space velocity is 0.1h ^-1~ 5.0h ^-1, average reaction temperature 280 DEG C ~ 465 DEG C.

8. method according to claim 1, is characterized in that: in step (c), and the reaction pressure of second segment reaction zone is 5.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is 400:1 ~ 2500:1, and volume space velocity is 0.1h ^-1~ 4.0h ^-1, average reaction temperature is 300 DEG C ~ 460 DEG C.

9. method according to claim 1, is characterized in that: first paragraph reaction zone liquid phase generates oil and accounts for 5% ~ 40% of second segment reaction zone liquid phase feeding weight.

10. the method according to claim 1 or 9, is characterized in that: first paragraph reaction zone liquid phase generates oil and accounts for 10% ~ 30% of second segment reaction zone liquid phase feeding weight.

11. methods according to claim 1, are characterised in that altogether: the DNA vaccine of first paragraph reaction zone bio-oil raw material controls to be 40% ~ 95%.

12. methods according to claim 11, are characterised in that altogether: the DNA vaccine of first paragraph reaction zone bio-oil raw material controls to be 60% ~ 90%.