CN103102967A

CN103102967A - Wax oil hydrotreating method for diesel oil by-production

Info

Publication number: CN103102967A
Application number: CN2011103537698A
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: 2013-05-15
Anticipated expiration: 2031-11-10
Also published as: CN103102967B

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 wax oil hydrogenation treatment process that can by-product diesel oil.

Background technology

The energy in global range is mainly derived from fossil energy at present, 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 the aggravation of in poor quality trend, and world economy sustainable development, environmental regulation increasingly stringent need to be produced a large amount of light clean fuels, increase new oil substitutes when these all require existing oil Refining Technologies is improved, produce satisfactory product with minimum cost.Catalytic cracking is one of important means of light materialization of heavy oil, but in poor quality and heaviness along with the catalyzed cracking processing raw material, its operational condition is more and more harsher, light-end products yield and product property variation, and the hydrotreating of FCC feedstock technology not only can be removed the content of desulfuration, nitrogen, metal impurities, also can improve the cracking performance of charging, reduce the FCC operating severity; Improve product and distribute, improve the purpose product selectivity; Reduce dry gas and coke yield, improve the economy of FCC apparatus; Reduce purpose product sulphur content; Reduce SOx and NOx content etc. in regenerated flue gas.

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

existing animal-plant oil hydrogenation method is produced 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 the vegetables oil hydroconversion process, adopt the coker gasoline cut, 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 the hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses vegetables oil such as containing unsaturated fatty acids, fat and animal oil mixing back end hydrogenation is produced the diesel oil blending component of diesel oil distillate scope.EP1741767 and EP1741768 disclose a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil and at first pass through hydrotreatment, then by the isomerization catalyst bed layer, obtain the low freezing point diesel fuel component, but owing to generating water in the hydrotreatment process, isomerization catalyst is caused very adverse influence, and device can not long-period stable operation.US20110155636 discloses a kind of hydroprocessing process that contains biomass material, and having used Fe system, Cu system, chromium is the catalyzer of metal and steam conversion.

For the wax oil hydrogenation treatment technology, be mainly the characteristics for the wax oil raw material, select the catalyst loading technology of grating and the operational condition of optimization, for catalytic cracking unit provides raw material after hydrogenation.CN200910204292.X discloses a kind of wax oil liquid phase circulation method of hydrotreating, CN101376840 and CN101376841 disclose a kind of heavy distillate oil hydrotreating method, CN10108913 discloses a kind of hydroprocessing process, US3983029 and US6793804 disclose wax oil hydrogenation treatment technology and catalyzer, the density 0845～0.870g/cm of the above-mentioned resulting diesel oil distillate of these method by-products ³Cetane value 40～50, sulphur content 51～1000 μ g/g, can not directly satisfy the requirement of the Europe IV standard or higher standard, and because this diesel oil distillate has passed through hydrogenation technique one time, the difficulty of its further hydrogenating desulfurization is also very large, therefore in some techniques, wax oil hydrogenation is processed 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, is mainly bio-oil directly to be mixed refine to VGO, then by the improve working method of character diesel oil of fractionation.But the H that generates in the course of processing of the method ₂O has very adverse influence to the wax oil hydrogenation catalyzer, and CO and the CO of the generation of bio-oil hydrogenation reaction ₂Performance to hydrogenation catalyst has a negative impact, simultaneous methanation reaction will increase considerably temperature rise, even reach uncontrollable degree, the final methane that generates is difficult to the discharge system, thereby greatly reduce the hydrogen dividing potential drop of reactive system, perhaps discharge methane by the method for discharging, so just increased considerably the hydrogen consumption of device.

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

Summary of the invention

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

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

(a) take the wax oil cut as stock oil, one or more in the bio-oil are as auxiliary material;

(b) under the hydroprocessing condition, bio-oil and recycle hydrogen are by the first paragraph reaction zone, the first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation activity component concentrations raise successively, bio-oil and hydrogen are at first by the low beds of hydrogenation activity component concentration, then by the high beds of hydrogenation activity component concentration, under response behaviour, the hydrogenation activity component is one or more in W, Mo, Ni and the Co of sulphided state;

(c) first paragraph reaction zone hydrogenation effluent separates the gas circulation use that obtains, and liquid phase generates oily entering with the wax oil feedstock and uses the second segment reaction zone of wax oil hydrogenation processing catalyzer to carry out the hydrotreatment reaction;

(d) gas phase of second segment reaction zone resultant gas liquid separation recycles, and liquid phase fractionation in separation column that second segment reaction zone liquid phase resultant gas liquid separates obtains petroleum naphtha, diesel oil and hydrogenation wax oil.

In the inventive method step (a), the bio-oil that uses 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.The wax oil distillate is mainly one or more mixing oils 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 condition 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, 180 ℃ ~ 425 ℃ of average reaction temperature; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 1.0h ^-1~ 4.0h ^-1, 200 ℃ ~ 400 ℃ of average reaction temperature.The deoxidation rate of first paragraph reaction zone bio-oil raw material is controlled to be 40%～95%, is preferably 60%～90%.

In the inventive method step (b), beds generally can arrange 2 ~ 5, in the beds that at first reaction mass passes through, the hydrogenation activity component is take the weight content of oxide compound as 3%～10%, the hydrogenation catalyst that at first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes of first paragraph reaction zone, preferred 20% ~ 70%, best 30% ~ 60%.The hydrogenation activity component concentration 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 simultaneously, as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.the business hydrogenation catalyst that the first reaction zone uses mainly contains, as 3926 of Fushun Petrochemical Research Institute (FRIPP) development, 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 is controlled higher than 0.005v%, and preferred 0.01v%～2.0v% to keep the stable sulfided state of catalyzer, keeps catalytic activity.Specifically can realize by the method for adding S-contained substance in reaction mass, also the circulation gas that contains hydrogen sulfide in step (c) can be circulated in step (b) and use.Contain water in first paragraph reaction zone hydrogenation effluent, can adopt suitable method to remove, as cooling rear separation removal.First paragraph reaction zone hydrogenation effluent separates the gas phase that obtains can be used at first paragraph reaction zone internal recycle, also can be used as the hydrogen make-up of second segment reaction zone.The gas phase that second segment reaction zone resultant gas liquid separates recycles at second reaction zone, also can be circulated on a small quantity the first reaction zone.

In the inventive method step (c), the hydroprocessing condition 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, 280 ℃ ~ 465 ℃ of average reaction temperature; 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, 300 ℃ ~ 460 ℃ of average reaction temperature.First paragraph reaction zone hydrogenation effluent need not lowered the temperature and be carried 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 simultaneously, as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.The business hydrogenation protecting agent that the second segment reaction zone uses mainly contains, the KG series protective material of the RF series protective material of the ICR series protective material of CHEVRON company exploitation and catalyst for demetalation, Uop Inc.'s exploitation, the RG series protective material of RIPP exploitation, AKZO company exploitation and the FZC series protective material of FRIPP exploitation and catalyst for demetalation etc.the business hydrotreating catalyst that the first paragraph reaction zone uses mainly contains, as 3926 of Fushun Petrochemical Research Institute (FRIPP) development, 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, ICR 179 hydrogenation catalysts such as 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 main hydrotreating catalyst that the second segment reaction zone uses can be the same catalyzer with the high metal content hydrogenation catalyst that the first paragraph reaction zone uses, and can not be also the same catalyzer.

In the inventive method, first paragraph and second segment reaction zone hydrogenation activity component are the catalyzer of oxidation state, carry out conventional sulfidizing before using, and make the hydrogenation activity component be converted into sulphided state, perhaps use the outer good catalyzer of prevulcanized of device.The wax oil feedstock can be the reduced pressure distillate that the crude oil underpressure distillation obtains.

In prior art, the bio-oil hydrogenation is produced the method for automotive fuel, generally need to petroleum fractions (gasoline, diesel oil, wax oil or the residual oil) hybrid process of larger proportion, perhaps directly by hydrofining-catalyst for hydro-upgrading bed, the H that reaction process generates ₂O, CO and CO ₂And CH ₄Deng can produce very adverse influence to existing hydrogenation catalyst system, affect the life-span of the device cycle of operation or catalyzer.The present invention uses grating technology and the operational condition of catalyzer by optimization, first paragraph hydrofining (hydrogenation catalyst of grating and control suitable bio-oil raw material deoxidation rate), second segment first paragraph hydrogenated oil and wax oil distillate mixed hydrogenation are processed, can be directly with by-product fine-quality diesel oil when producing the hydrogenation wax oil, have to wax oil hydrogenation processing catalysts influence the advantages such as little, device cycle of operation length.Control suitable deoxidation rate in bio-oil hydrogenation process, be conducive to simultaneously the stability of bio-oil hydrogenation process and the stability of wax oil hydrogenation treating processes.

Description of drawings

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 the hydroprocessing condition by comprising the first paragraph hydroconversion reaction zone of at least two kinds of hydrogenation catalysts, the hydrogenated oil that obtains high-pressure separator (abbreviation high score) separate the gas obtain mixes with the gas phase of second segment reaction zone reaction product dewater with the depriving hydrogen sulphide processing after recycle, the liquid distillate that obtains and wax oil distillate and recycle hydrogen are mixed into and comprise the second segment reaction zone that serial wax oil hydrogenation is processed catalyzer, obtaining the hydrotreatment logistics recycles at second segment at the gas that high-pressure separator (abbreviation high score) separation obtains, the liquid fractionation that obtains obtains following products: gas, petroleum naphtha, fine-quality diesel oil and hydrogenation wax oil.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.

Further illustrate particular case of the present invention below by embodiment.The first paragraph reaction zone of embodiment 1 and embodiment 2 uses the part recycle hydrogen (as Fig. 2 flow process) of second segment reaction zone, and embodiment 3 first paragraph reaction zones use vulcanizing agent to keep hydrogen sulfide content (as Fig. 1 flow process).

The chief component 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	The reference example	Embodiment 2	Embodiment 3
					Catalyzer	Catalyzer 1/ catalyzer 3	?	Catalyzer 1/ catalyzer 2/ catalyzer 3	Catalyzer 1/ catalyzer 2
The 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
					The entrance hydrogen to oil volume ratio	1000:1	?	1000:1	1000:1
The cumulative volume air speed, h ^-1	3.3	?	1.5	5.0
					Average reaction temperature, ℃	325	?	340	330
Vulcanizing agent	DMDS	?	DMDS	DMDS
					Hydrogen sulfide content, v%	0.10	?	0.10	0.10
First paragraph reaction zone deoxidation rate, %	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
					The 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
The 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, ℃	390	390	385	370
					CO+CO in circulation gas turned round after 200 hours ₂+CH ₄, volume %	3.9	8.7	3.4	2.1
The 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

Can be found out by embodiment, the wax oil hydrogenation treatment process by present technique can be under the prerequisite of producing the hydrogenation wax oil by-product fine-quality diesel oil product, and can realize long-period stable operation.The inventive method has promoter action to the wax oil hydrogenation processing reaction simultaneously, in the situation that close desulfurization degree, the inventive method can operate under higher air speed, and namely the treatment capacity of device can obviously improve.

Claims

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

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

3. method according to claim 1, it is characterized in that: in step (b), 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, 180 ℃ ~ 425 ℃ of average reaction temperature.

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, 200 ℃ ~ 400 ℃ of average reaction temperature.

5. according to claim 1 or 3 described methods, it is characterized in that: in step (b), first paragraph reaction zone beds arranges 2 ~ 5, in the beds that at first reaction mass passes through, the hydrogenation activity component is take the weight content of oxide compound as 3%～10%, and the hydrogenation catalyst that at first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes of first paragraph reaction zone; The hydrogenation activity component of the downstream catalyst that reaction mass passes through increases by 3～25 percentage points in oxide weight than adjacent upstream catalyzer.

6. method according to claim 5, it is characterized in that: in step (b) first paragraph reaction zone, the hydrogenation catalyst that at first reaction mass passes through accounts for 20% ~ 70% of all hydrogenation catalyst volumes of first paragraph reaction zone; The hydrogenation activity 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, it is characterized in that: in step (c), 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, 280 ℃ ~ 465 ℃ of average reaction temperature, preferred reaction pressure is that 5.0MPa ~ 18.0MPa hydrogen to oil volume ratio is 400:1 ~ 2500:1, volume space velocity is 0.1h ^-1~ 4.0h ^-1, average reaction temperature is 300 ℃ ~ 460 ℃.

8. method according to claim 1, is characterized in that: oily 5%～40% of the second segment reaction zone liquid phase feeding weight that accounts for of first paragraph reaction zone liquid phase generation.

9. according to claim 1 or 8 described methods, is characterized in that: oily 10%～30% of the second segment reaction zone liquid phase feeding weight that accounts for of first paragraph reaction zone liquid phase generation.

10. method according to claim 1, be characterised in that altogether: the deoxidation rate of first paragraph reaction zone bio-oil raw material is controlled to be 40%～95%, is preferably 60%～90%.