CN103102900B

CN103102900B - Hydrogenation method for producing high quality solvent oil from biological oil

Info

Publication number: CN103102900B
Application number: CN201110353623.3A
Authority: CN
Inventors: 刘涛; 白振民; 李宝忠; 赵玉琢; 孙士可
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: 2015-01-14
Anticipated expiration: 2031-11-10
Also published as: CN103102900A

Abstract

The present invention relates to a hydrogenation method for producing a high quality solvent oil from a biological oil. The method is characterized in that a biological oil is adopted as a raw material oil; under a hydrogenation operation condition, the raw material oil and hydrogen gas pass through a first stage hydrogenation reaction zone containing at least two hydrogenation reactors, wherein the raw material oil and the hydrogen gas sequentially pass through a low temperature operation reactor and a high temperature operation reactor; hydrogen-rich gas separated from the stream generated from hydrogenation is recycled, and the separated liquid enters a second stage hydrocracking reaction zone; sub-hydrogen gas separated from the stream generated from hydrocracking is recycled, and the separated liquid product is subjected to fractionation to obtain various high quality solvent oils; and under a reaction state, active components of the hydrogenation catalysts used at the first stage and the second stage are reduction state Pt and/or Pd. Compared to the method in the prior art, the method of the present invention has the following advantages that: high quality solvent oil production methods are increased, activity stability of the catalyst can be ensured, and stable and long period device operation can be ensured.

Description

The method of hydrotreating of bio-oil production high-quality solvent oil

Technical field

The present invention relates to a kind of method of hydrotreating, particularly a kind of is stock oil with bio-oil, the method for hydrotreating of direct production high-quality solvent oil.

Background technology

World economy sustainable development, in current global range, the main source of Chemicals is fossil energy, wherein most importantly oil and coal.These two kinds of fossil energies all belong to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, difficulty of processing and tooling cost increase gradually, new oil substitutes is found except carrying out existing oil Refining Technologies improving, produce satisfactory product with minimum cost, especially the development and utilization of renewable resources obtains paying attention to more and more widely.

Bio-oil is as renewable resources, and main composition is carbon, hydrogen and oxygen, very similar to the composition of alkane, alcohol, ether etc., 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 low freezing point diesel fuel cut with animal-plant oil.

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, needs more catalyst changeout of often stopping work, and the main purpose product of these technology is automotive fuel.

Solvent oil is important petroleum products, and its added value is higher than fuel product, and particularly the added value of high-grade low aromatic solvent naphtha is higher.The low aromatic solvent naphtha raw materials for production of current top grade are limited (is generally only limitted to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, or reforming raffinate oil etc.), owing to requiring aromaticity content lower (some solvent oil index request aromaticity content is lower than 0.1%), therefore need to adopt complicated processing route, condition is harsh, production cost is high, limits the production of high-grade low aromatic solvent naphtha.

In prior art, bio-oil usually passes through separately or produces the method for automotive fuel with the method for other petroleum products mixing back end hydrogenations.The present invention is by optimizing the grating technology and operational condition that use noble metal hydrogenation catalyst, and first paragraph hydrofining (hydrogenation catalyst of grating), second segment hydrocracking can be directly raw material production low aromatic solvent naphtha with bio-oil.The present invention extends the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can improve added value of product further.

Summary of the invention

For the deficiencies in the prior art, the invention provides the method for hydrotreating that a kind of bio-oil produces low aromatic solvent naphtha, can be separately stock oil with bio-oil, use noble metal hydrogenation catalyst, the method of direct production high-quality low aromatic solvent naphtha under the condition of hydrogenation, there is hydrogenation process stablize, the features such as running period is long.

The method of hydrotreating of bio-oil production high-quality solvent oil of the present invention comprises following content:

A one or more in () bio-oil are stock oil;

B () is under Hydroprocessing conditions, stock oil and hydrogen pass through the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is Pt and/or Pd of reduction-state;

C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration process Posterior circle uses, the second segment reaction zone using hydrocracking catalyst is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of hydrocracking catalyst is Pt and/or Pd of reduction-state;

D the gas phase of () second segment reaction zone reaction effluent recycles, liquid phase fractionation in separation column of second segment reaction zone reaction effluent obtains low aromatic solvent naphtha.

In the inventive method step (a), the bio-oil used 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.

In the inventive method step (b), the Hydroprocessing conditions of the hydrotreating reactor of cold operation is generally reaction pressure 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h ^-1~ 6.0h ^-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 2.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h ^-1~ 6.0h ^-1, average reaction temperature is higher than the hydrotreating reactor of cold operation 50 DEG C ~ 300 DEG C, preferably high 80 ~ 220 DEG C.Process furnace or interchanger are set between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, to adjust the temperature of reaction of the hydrotreating reactor of high-temperature operation.

Reaction mass is first by the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%.Reaction mass continues through the hydrogenator of high-temperature operation, and the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.10% ~ 3.50%.In the hydrogenator of preferred high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrogenator, preferably high 0.1 ~ 3 percentage point (in element quality).Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also can load multiple catalysts.

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.Noble metal catalyst such as Fushun Petrochemical Research Institute (FRIPP) develops HDO-18 catalyzer, also can by described method preparations such as CN00123141.3.

In the inventive method step (b), catalyzer uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, reduces under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.

In the inventive method step (c), the Hydroprocessing conditions of second segment reaction zone is generally reaction pressure 2.0MPa ~ 20.0MPa, usually (pressure rating that identical finger herein identical identical with first paragraph reaction zone, due to the Pressure Drop of Flow of Goods and Materials, second segment reaction zone reaction pressure can a little less than first paragraph reaction zone), hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h ^-1~ 6.0h ^-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h ^-1~ 4.0h ^-1, average reaction temperature 200 DEG C ~ 445 DEG C.

In the inventive method step (c), the hydrocracking catalyst of second segment reaction zone has cracking function, as containing the component such as Y zeolite and/or ZSM-5 molecular sieve.Hydrocracking catalyst is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.5%.The weight content of molecular sieve component in hydrocracking catalyst is generally 5% ~ 60%.Hydrocracking catalyst can use commercial goods catalyzer, also can prepare by this area ordinary method.

In the inventive method step (d), the low aromatic solvent naphtha obtained is mixed solvent oil distillate, fractionation can be continued according to the actual requirements and obtain vegetable oil extraction solvent, No. 90 solvent oils, No. 120 solvent oils, No. 200 trade mark such as solvent oil, D30, D40 low aromatic solvent naphthas, specifically can determine according to the character of mixed solvent oil distillate.

In the inventive method step (d), at low conversion rate in 100% time, the unconverted oil fractionated out in separation column can loop back first paragraph reaction zone or second segment reaction zone, preferred cycle goes back to second segment reaction zone, and the quality looping back the unconverted oil of reactive system is 5 ~ 50% of fresh feed (raw material of first paragraph reaction zone).

In the inventive method, catalyzer uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, reduces under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.

In the inventive method, Hydrobon catalyst can be supplemented in right amount, by material hydrogenation such as issuable a small amount of rare hydrocarbon in hydrocracking process finally arranging of hydrocracking catalyst bed.

Accompanying drawing explanation

Fig. 1 is the method for hydrotreating principle flow chart of bio-oil production high-quality solvent oil of the present invention.

Embodiment

Method of the present invention is specific as follows: with the mixing oil of one or more in bio-oil for stock oil, under Hydroprocessing conditions, stock oil and hydrogen pass through low temperature and the high temperature hydrogenation reactor of loading catalyst, the hydrogenated oil obtained is separated in high-pressure separator (abbreviation high score) gas circulation obtained and uses, also system can be gone out, the liquid fractionation obtained and hydrogen are mixed into the second segment reaction zone comprising and have cracking performance hydrocracking catalyst, obtain hydrocracking logistics and be separated the gas circulation use obtained in high-pressure separator (abbreviation high score), the liquid fractionation obtained obtains various high-quality low aromatic solvent oil production, during low conversion rate, unconverted oil is circulated to second segment reaction zone.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 main composition of table 1 hydrogenation catalyst and character.

Catalyzer	Catalyzer 1	Catalyzer 2	Catalyzer 3	Cracking catalyst 1	Cracking catalyst 2
						Catalyzer forms	?	?	?	?	?
Pt，wt%	0.4	1.2	0.05	1.0	0.8
						Pd，wt%	0.1	?	0.1	0.1	0.15
ZSM-5 molecular sieve, wt%	?	?	?	13.6	?
						Y molecular sieve, wt%	?	?	?	?	20.5
Alumina supporter, wt%	Surplus	Surplus	Surplus	Surplus	Surplus
						The main character of catalyzer	?	?	?	?	?
Specific surface, m ²/g	>160	>160	>160	>160	>160
						Pore volume, ml/g	0.33	0.32	0.35	0.34	0.34

Table 2 embodiment processing condition and test-results.

Processing condition	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					Stock oil	Soybean oil	Rapeseed oil	Tung oil	Oleum Gossypii semen
First paragraph reaction zone operational condition	?	?	?	?
					Cold operation reactor	?	?	?	?
Catalyzer	Catalyzer 3	Catalyzer 3/ catalyzer 1	Catalyzer 3/ catalyzer 1	Catalyzer 3
					Catalyst volume ratio	100	20:80	50:50	100
Reaction pressure, MPa	17.0	5.0	10.0	12.0
					Entrance hydrogen to oil volume ratio	2000:1	300:1	1000:1	800:1
Volume space velocity, h ^-1	2.0	1.5	0.8	0.4
					Average reaction temperature, DEG C	150	190	130	100
High-temperature operation reactor	?	?	?	?
					Catalyzer	Catalyzer 1	Catalyzer 1	Catalyzer 2	Catalyzer 2
Reaction pressure, MPa	17.0	5.0	10.0	12.0
					Entrance hydrogen to oil volume ratio	2000:1	300:1	1000:1	1000:1
Volume space velocity, h ^-1	1.0	1.8	0.5	2.5
					Average reaction temperature, DEG C	360	320	280	380
Per pass conversion, quality %	90	75	85	100
					Second segment reaction zone operational condition	?	?	?	?
Stock oil	First paragraph product liquid	First paragraph product liquid	First paragraph product liquid+20% unconverted oil	First paragraph product liquid
					Catalyzer	Cracking catalyst 1	Cracking catalyst 1	Cracking catalyst 2	Cracking catalyst 2
Reaction pressure, MPa	17.0	5.0	10.0	12.0
					Entrance hydrogen to oil volume ratio	1500	500	800	1000
Volume space velocity, h ^-1	2.0	4.5	1.5	3.5
					Average reaction temperature, DEG C	320	370	280	290
Spirit fraction	?	?	?	?
					Yield, quality %	88	82	84	89
Aromaticity content	Do not detect	Do not detect	Do not detect	Do not detect
					Sulphur content, μ g/g	Do not detect	Do not detect	Do not detect	Do not detect
Boiling range scope, DEG C	65～174	63～150	62～120	62～145

Table 3 embodiment processing condition and test-results.

Processing condition	Embodiment 5	Comparative example 1	Comparative example 2	Comparative example 3
					Stock oil	Tung oil	Tung oil	Tung oil	Tung oil
Cold operation reactor	?	?	?	?
					Catalyzer	Catalyzer 3	?	?	?
Reaction pressure, MPa	8.0	?	?	?
					Entrance hydrogen to oil volume ratio	2000:1	?	?	?
Volume space velocity, h ^-1	2.5	?	?	?
					Average reaction temperature, DEG C	180	?	?	?
High-temperature operation reactor	?	?	?	?
					Catalyzer	Catalyzer 2	Catalyzer 2/ cracking catalyst 1	Catalyzer 2/ cracking catalyst 1	Catalyzer 2/ cracking catalyst 1
Reaction pressure, MPa	8.0	8.0	8.0	8.0
					Entrance hydrogen to oil volume ratio	1000:1	1000:1	1000:1	1000:1
Volume space velocity, h ^-1	0.8	0.5	0.5	0.5
					Average reaction temperature, DEG C	310	310	310	320
Two step process condition	?	—	—	—
					Catalyzer	Cracking catalyst 1	?	?	?
Reaction pressure, MPa	10.0	?	?	?
					Entrance hydrogen to oil volume ratio	1000:1	?	?	?
Cumulative volume air speed, h ^-1	2.8	?	?	?
					Average reaction temperature, DEG C	310	?	?	?
Runtime, h	1000	200	400	600
					Spirit fraction	?	?	?	?
Yield, quality %	85	85	61	44
					Aromaticity content	Do not detect	Do not detect	Do not detect	Do not detect
Sulphur content, μ g/g	Do not detect	Do not detect	Do not detect	Do not detect
					Boiling range scope, DEG C	61～160	65～160	65～160	65～160

Yield with second segment reaction zone feeds for benchmark.The consumption of comparative example catalyzer 2 is identical with total consumption of catalyzer 3 with catalyzer 2 in embodiment 5, and comparative example cracking catalyst 1 consumption is identical with cracking catalyst consumption in embodiment 5.

As can be seen from embodiment, bio-oil can direct production various high-quality low aromatic solvent oil production by the method for hydrotreating of this technology, by selecting different bio-oils, can production high-quality low aromatic solvent naphtha, and running is stable.

Claims

1. a method of hydrotreating for bio-oil production high-quality solvent oil, is characterized in that comprising following content:

A one or more in () bio-oil are stock oil;

B () is under Hydroprocessing conditions, stock oil and hydrogen pass through the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is Pt and/or Pd of reduction-state, in the hydrogenator of the cold operation that first reaction mass passes through, the active ingredient of the hydrogenation catalyst used is in the element quality of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%, reaction mass continues through the hydrogenator of high-temperature operation, and the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.10% ~ 3.50%,

D the gas phase of () second segment reaction zone reaction effluent recycles, liquid phase fractionation in separation column of second segment reaction zone reaction effluent obtains low aromatic solvent oil distillate.

2. in accordance with the method for claim 1, it is characterized in that: in step (a), the bio-oil of use comprises vegetables oil or animal grease.

3. in accordance with the method for claim 1, it is characterized in that: in step (b), the reaction pressure 2.0MPa ~ 20.0MPa of the hydrotreating reactor of cold operation, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h ^-1~ 6.0h ^-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 2.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h ^-1~ 6.0h ^-1, average reaction temperature is higher than the hydrotreating reactor of cold operation 50 DEG C ~ 300 DEG C.

4. according to the method described in claim 1 or 3, it is characterized in that: in step (b), the average reaction temperature of the hydrotreating reactor of high-temperature operation is higher than the hydrotreating reactor of cold operation 80 DEG C ~ 220 DEG C.

5. in accordance with the method for claim 4, it is characterized in that: in the hydrogenator of high-temperature operation, the active component content of catalyzer is in element quality, higher than the catalyzer in cold operation hydrogenator 0.1 ~ 3 percentage point.

6. according to the method described in claim 1 or 3, it is characterized in that: the first paragraph reaction zone in step (b) arranges 2 ~ 5 reactors.

7. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h ^-1~ 6.0h ^-1, average reaction temperature 180 DEG C ~ 465 DEG C.

8. in accordance with the method for claim 1, it is characterized in that: in step (c), the operation condition hydrogen to oil volume ratio of second segment reaction zone is 300:1 ~ 2500:1, and volume space velocity is 0.4h ^-1~ 4.0h ^-1, average reaction temperature is 200 DEG C ~ 445 DEG C.

9. according to the method described in claim 1 or 8, it is characterized in that: in step (c), the hydrocracking catalyst of second segment reaction zone has cracking function, hydrocracking catalyst contains Y zeolite and/or ZSM-5 molecular sieve component, hydrocracking catalyst is in the element quality of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.5%, and the weight content of molecular sieve component in hydrocracking catalyst is 5% ~ 60%.

10. in accordance with the method for claim 1, it is characterized in that: in step (d), unconverted turning oil is circulated to first paragraph reaction zone, or is circulated to second segment reaction zone, and turning oil accounts for 5% ~ 50% of fresh feed quality.

11. in accordance with the method for claim 1, it is characterized in that: in step (d), and unconverted turning oil is circulated to second segment reaction zone.