CN103102960A

CN103102960A - Residue oil hydrogenation method for diesel oil by-production

Info

Publication number: CN103102960A
Application number: CN2011103537005A
Authority: CN
Inventors: 李洪广; 彭湃; 张晔; 吴锐; 蒋立敬; 韩照明; 耿新国; 张庆军
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: CN103102960B

Abstract

The present invention relates to a residue oil hydrogenation 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 adopted as second stage supply hydrogen to be used, the separated liquid and the residual oil are mixed and enter a second stage residual oil hydrogenation reaction zone, the sub-hydrogen separated from the oil generated through second stage hydrogenation is recycled at the second stage, and the separated liquid product is subjected to fractionation to obtain naphtha, high quality diesel oil and hydrogenation residual 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 residual oil hydrogenation method of the present invention has the following characteristics that: the high quality diesel oil can be by-produced on the residual oil hydrogenation device, activity stability of the catalyst is good, and the device can stably operate for a long period.

Description

The residual hydrogenation method of by-product diesel oil

Technical field

The present invention relates to a kind of method of hydrotreating, particularly a kind of residual hydrogenation method of by-product fine-quality 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.Conversion for residual oil mainly contains residual hydrogenation and two kinds of approach of coking, and wherein residual hydrogenation is the important technology of producing clean fuel, and hydrogenated residue provides the high-quality charging for catalytic cracking, can reduce SO in catalytic cracking unit operating process flue gas _xAnd NO _xDischarging, and increase light oil yield and effectively reduce sulphur content in catalytic gasoline.

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.

For the residual hydrogenation technology, be mainly the characteristics for residual oil, select the catalyst loading technology of grating and the operational condition of optimization, for catalytic cracking unit provides raw material after hydrogenation.CN200810246649.6 discloses a kind of method of hydrotreating of residual oil, CN200610007532.3 discloses a kind of method of hydrotreating of producing catalytically cracked material, CN02133138.3 discloses a kind of heavy hydrocarbon hydroprocessing method, CN01114166.2 discloses a kind of process for hydrogenating residual oil, US20050311134 discloses a kind of hydrogenating conversion process of heavy residual oil, EP19930201257 discloses a kind of hydroprocessing process, be the hydroprocessing process of residue oil fraction, the density 0845～0.870g/cm of the diesel product of these method by-products ³, cetane value 40～48, sulphur content 100～600 μ g/g can not satisfy the requirement of the Europe IV standard or higher standard.In addition, the method of carrying out upgrading for the diesel oil of residual hydrogenation by-product is mainly CN01123761.9 and discloses a kind of method that reduces aromatic content of diesel oil in residual hydrogenation equipment, the method is only that the diesel oil to by-product carries out hydrogenation aromatics-removing, there is no the introducing of renewable raw materials, increased process cost.

CN200910187930.1 discloses a kind of method that the refining bio-oil improves residual hydrogenation of mixing, and is mainly bio-oil directly to be mixed refine to residual hydrogenation equipment, then by the improve working method of character of fractionation.But the H that generates in production process ₂O has adverse influence to residual oil hydrocatalyst, and reaction generates CO and CO ₂Catalyst performance is exerted an influence, and methanation reaction can occur, the methane of generation is difficult to the discharge system, thereby greatly reduces the hydrogen dividing potential drop of reactive system, perhaps discharges methane by the method for discharging, has increased considerably like this 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 residual oil as stock oil by-product diesel oil, at first bio-oil passes through filling hydrogenation catalyst first paragraph reaction zone with new hydrogen, then liquid and residual oil are mixed into the second segment reaction zone of filling residual hydrogenation catalyst series, can direct production fine-quality diesel oil and hydrogenated residue, have hydrogenation process stable, running period is long, and the residual hydrogenation reaction zone is affected the characteristics such as little.

The residual hydrogenation method of by-product fine-quality diesel oil of the present invention comprises following content:

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

(b) under the hydroprocessing condition, bio-oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in hydrogenator, bio-oil and hydrogen is the hydrogenator by cold operation at first, then the hydrogenator by high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and the Co of sulphided state;

(c) first paragraph reaction zone hydrogenation effluent separates the gas phase obtain and recycles, and liquid phase generates oil and enters with residual oil raw material the second segment reaction zone that uses catalyst for hydrotreatment of residual oil and 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 resultant gas liquid separates obtains petroleum naphtha, diesel oil and hydrogenated residue.

In the inventive method step (a), the bio-oil that uses can comprise vegetables oil 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.Residual oil can be long residuum or vacuum residuum, also can mix other close cuts of other cut scopes.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 the hydrotreating reactor of cold operation 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~ 6.0h ^-1, 120 ℃ ~ 280 ℃ of average reaction temperature; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.5h ^-1~ 6.0h ^-1, average reaction temperature than the hydrotreating reactor of cold operation high 50 ℃ ~ 300 ℃, preferred high 80 ~ 220 ℃.Between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, process furnace or interchanger are set, with the temperature of reaction of the hydrotreating reactor of adjusting high-temperature operation.

Bio-oil is at first by in the hydrogenator of cold operation, and the hydrogenation activity component is take the weight content of oxide compound as 3%～10%.Can use the multiple catalysts grating to use in the hydrogenator of cold operation.In the hydrogenator of high-temperature operation, the active component content of catalyzer is in the element quality, higher than 3～25 percentage points of the catalyzer in the cold operation hydrogenator.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 8.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h ^-1~ 4.0h ^-1, 280 ℃ ~ 465 ℃ of average reaction temperature; Preferred operational condition is reaction pressure 10.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 500:1 ~ 2500:1, volume space velocity 0.1h ^-1~ 2.0h ^-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 residual hydrogenation catalyst series of second segment reaction zone can use the hydrogenation catalyst of this area routine, specifically can comprise protective material, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrification (taking off carbon residue) catalyzer etc., mainly contain ICR series protective material and the ICR catalyst series of the exploitation of CHEVRON company, RM series and the RN catalyst series of the exploitation of CRITERION company, the RF series protective material of Uop Inc.'s exploitation, RF catalyst series and RCD catalyst series, KG series protective material and the KFR catalyst series of the exploitation of AKZO company, TK series protective material and the TK catalyst series of the exploitation of Haldor Topsoe company, RG series protective material and the RDM of RIPP exploitation, RMS, the RSN catalyst series, FZC series protective material and the FZC catalyst series of FRIPP exploitation, as: FZC-100, FZC-101, FZC102, FZC-103, FZC104, FZC-105, FZC106, FZC10, FZC-11, FZC12, FZC13, FZC-14, the protective materials such as FZC15, FZC-201, FZC202, FZC-203, FZC-204, FZC-21, FZC22, FZC-23, the Hydrodemetalation catalysts such as FZC-24, FZC301, FZC-302, FZC-303, FZC31, FZC-32, FZC-33, the Hydrobon catalysts such as FZC-34, FZC-40, FZC-41, the hydrodenitrifications such as FZC-41A (taking off carbon residue) catalyzer etc.

In the inventive method step (c), first paragraph reaction zone and second segment reaction zone hydrogenation activity component are the catalyzer of oxidation state, carry out conventional sulfidizing before using, make the hydrogenation activity component be converted into sulphided state, perhaps use the outer good catalyzer of prevulcanized of device.

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 (the reduction-state hydrogenation catalyst of grating and control suitable bio-oil raw material deoxidation rate), second segment first paragraph hydrogenated oil and residual oil mixed hydrogenation are processed, can be directly with by-product fine-quality diesel oil when producing hydrogenated residue, have on the residual oil hydrocatalyst impact 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 residual hydrocracking process.

Description of drawings

Fig. 1 is the residual hydrogenation methodological principle schema of high-output qulified diesel oil of the present invention.

Fig. 2 is another principle flow chart of the residual hydrogenation method of high-output qulified 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 residual oil and recycle hydrogen are mixed into the second segment reaction zone that comprises serial residual oil hydrocatalyst, 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 hydrogenated residue.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 3 uses the part recycle hydrogen (as Fig. 2 flow process) of second segment reaction zone, and embodiment 2 first paragraph reaction zones use vulcanizing agent to keep hydrogen sulfide content (as Fig. 1 flow process).

Chief component and the character of table 1 first paragraph hydrogenation catalyst.

Catalyzer	Catalyzer 1	Catalyzer 2	Catalyzer 3	Catalyzer 4
					Catalyzer forms	?	?	?	?
MoO ₃，wt%	3.4	8.0	16.5	26.1
					CoO，wt%	0.6	?	3.8	?
NiO，wt%	?	2.8	?	5.2
					Alumina supporter, wt%	Surplus	Surplus	Surplus	Surplus
The main character of catalyzer	?	?	?	?
					Specific surface, m ²/g	>160	>160	>160	>160
Pore volume, ml/g	>0.30	>0.30	>0.30	>0.30

Chief component and the character of table 2 second segment residual hydrogenation catalyst series.

Catalyzer

HB1

HB2

HDM1

HDM2

HDS

HDC

Catalyzer forms

?

MoO ₃，wt%

3.4

7.5

10.0

15.1

20.5

25.5

NiO，wt%

1.0

2.5

3.1

?

4.4

5.3

CoO，wt%

?

3.5

?

Alumina supporter, wt%

Surplus

The main character of catalyzer

?

Specific surface, m ²/g

>100

>110

>130

>150

>160

Pore volume, ml/g

0.80

0.75

0.60

0.55

0.40

>0.35

Proportioning, volume %

2

8

10

15

28

37

Annotate: HB refers to protective material, and HDM refers to Hydrodemetalation catalyst, and HDS refers to Hydrobon catalyst, and HDC refers to the removal of ccr by hydrotreating catalyzer.

Table 3 stock oil main character.

Stock oil	Normal slag 1	Normal slag 2	Soybean oil	Plam oil
					S，wt%	4.0	2.5	<0.001	<0.001
N，wt%	0.280	0.200	<0.001	<0.001
					Carbon residue, wt%	11.9	8.0	—	—
Ni+V，μg/g	120	80	0	0

Table 4 embodiment and reference example processing condition and test-results.

?	Embodiment 1	The reference example	Embodiment 2	Embodiment 3
					Stock oil	Plam oil	?	Soybean oil	Plam oil
First paragraph reaction zone operational condition	?	?	?	?
					The cold operation reactor	?	?	?	?
Catalyzer	Catalyzer 1/ catalyzer 2	?	Catalyzer 1/ catalyzer 2	Catalyzer 1/ catalyzer 2/ catalyzer 3
					The catalyst volume ratio	30:70	?	25:75	10:30:60
Reaction pressure, MPa	15.0	?	4.0	15.0
					The entrance hydrogen to oil volume ratio	1000:1	?	1500:1	700:1
The cumulative volume air speed, h ^-1	5.0	?	3.5	4.0
					Average reaction temperature, ℃	220	?	240	260
The high-temperature operation reactor	?	?	?	?
					Catalyzer	Catalyzer 3	?	Catalyzer 3/ catalyzer 4	Catalyzer 4
The catalyst volume ratio	100	?	40:60	100
					Reaction pressure, MPa	15.0	?	4.0	15.0
The entrance hydrogen to oil volume ratio	1000:1	?	1500:1	800:1
					The cumulative volume air speed, h ^-1	5.0	?	2.0	4.0
Average reaction temperature, ℃	320	?	330	340
					Vulcanizing agent	?	?	DMDS	?
Hydrogen sulfide content, v%	?	?	0.1	?
					First paragraph reaction zone deoxidation rate, %	75	?	80	75
Second segment reaction zone processing condition	?	?	?	?
					Catalyzer	Table 2 proportioning	Table 2 proportioning	Table 2 proportioning	Table 2 proportioning
Stock oil, weight	85% residual oil 1+15% first paragraph generates oil	85% residual oil 1+15% plam oil	90% residual oil 1+10% first paragraph generates oil	80% residual oil 2+20% first paragraph generates oil
					Reaction pressure, MPa	15.0	15.0	15.0	15.0
The entrance hydrogen to oil volume ratio	1000:1	1000	500:1	800:1
					Volume space velocity, h ^-1	0.37	0.25	0.25	0.30
Average reaction temperature, ℃	390	390	375	395
					CO+CO in circulation gas turned round after 200 hours ₂+CH ₄, volume %	3.0	9.5	1.9	3.3
The hydrogenated diesel oil product	?	?	?	?
					Yield, wt%	28.3	27.6	29.6	23.9
Density, g/cm ³	0.830	0.831	0.829	0.832
					Sulphur content, μ g/g	85	87	95	47
Cetane value	71	67	61	76
					The hydrogenated residue product	?	?	?	?
Sulphur content, μ g/g	3050	3100	3000	1900
					Nitrogen content, μ g/g	1250	1270	1100	550
Carbon residue, %	5.1	5.5	4.5	2.6
					Metal (Ni+V), μ g/g	11.5	11.8	10.6	5.0

Can be found out by embodiment, the residual hydrogenation method by present technique can be under the prerequisite of producing hydrogenated residue by-product fine-quality diesel oil product, and can realize long-period stable operation.

Claims

1. the residual hydrogenation method 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 or animal grease.

3. method according to claim 1, it is characterized in that: in step (b), the reaction pressure 3.0MPa of the hydrotreating reactor of cold operation ~ 20.0MPa, hydrogen to oil volume ratio are 200:1 ~ 3000:1, and volume space velocity is 0.5h ^-1~ 6.0h ^-1, 120 ℃ ~ 280 ℃ of average reaction temperature; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.5h ^-1~ 6.0h ^-1, average reaction temperature than the hydrotreating reactor of cold operation high 50 ℃ ~ 300 ℃.

4. in accordance with the method for claim 1, it is characterized in that: in step (b), the average reaction temperature of the hydrotreating reactor of high-temperature operation is higher 80 ~ 220 ℃ than the hydrotreating reactor of cold operation.

5. according to claim 1 or 3 described methods is characterized in that: in step (b), in the hydrogenator of the cold operation that at first reaction mass passes through, the hydrogenation activity component is take the weight content of oxide compound as 3%～10%.

6. in accordance with the method for claim 5, it is characterized in that: in the hydrogenator of high-temperature operation, the active component content of catalyzer is in the element quality, higher than 3 ~ 25 percentage points of the catalyzer in the cold operation hydrogenator.

7. method according to claim 1, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 8.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 3000:1, and volume space velocity is 0.1h ^-1~ 4.0h ^-1, 280 ℃ ~ 465 ℃ of average reaction temperature, preferred reaction pressure is that 10.0MPa ~ 20.0MPa hydrogen to oil volume ratio is 500:1 ~ 2500:1, volume space velocity is 0.1h ^-1~ 2.0h ^-1, average reaction temperature is 300 ℃ ~ 460 ℃.

8. method according to claim 1, it is characterized in that: in step (c), the residual hydrogenation catalyst series of second segment reaction zone comprises protective material, Hydrodemetalation catalyst, Hydrobon catalyst and removal of ccr by hydrotreating catalyzer.

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, is preferably 10%～30%.

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%.