CN205443198U - Utilize living beings oil production green transport fuel's combination hydrogenated apparatus;hydrogenated unit - Google Patents
Utilize living beings oil production green transport fuel's combination hydrogenated apparatus;hydrogenated unit Download PDFInfo
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Abstract
The utility model relates to an utilize living beings oil production green transport fuel's combination hydrogenated apparatus, hydrogenated unit, living beings oil preprocessor, one section high temperature hydrogenation fixed bed reactor, one section reaction product vapour and liquid separator, two -stage process high temperature hydrogenation fixed bed reactor, two -stage process reaction product vapour and liquid separator and air distillation tower that the device links to each other including the order, the device still includes the hydrogen supply system. The device provided by the utility model using and making up the formula system as raw materials, adoption two -stage hydrogenation by palingenetic living beings oil, can obtain the direct green transport fuel who uses the mixing of inclusive AND fossil class transport fuel, the flow is simple, and the power consumption is hanged down, has extremely strong practical spreading value.
Description
Technical field
This utility model relates to bio-oil hydrogen addition technology field, is specifically related to a kind of combined hydrogenation device utilizing bio-oil to produce environmental protection transport fuel.
Background technology
Along with fossil resource consumes rapidly, skyrocketing of use cost, ecological environment constantly deteriorates, and ensures that energy security, reply climate change have become the focal issue in the whole world.Countries in the world all accelerated development regenerative resources, particularly biomass energy.Biomass are the Organic substances that organism synthesizes through photosynthesis, are to be directly produced gas, liquid, the Renewable resource of the solid energy.The stock number of biomass is the hugest, bio-fuel be can replacing gasoline and the regenerative resource of diesel oil on a large scale, be also the important channel of petroleum replacing chemical products.
There is the disadvantage that structure is single, external dependence degree is high in China's energy-consuming, raw coal consumption accounting more than 60%, is the first in the world big coal production state and country of consumption, and within 2013, dependence on foreign countries for oil reaches 58.1%.Add up according to China's " planning of regenerative resource Long-and Medium-term Development ", China's biomass resource can be exchanged into about 500,000,000 tons of standard coals of potentiality of the energy, expansion and the development of economic society along with afforestation area, China's biomass resource is converted to the potentiality of the energy up to 1,000,000,000 tons of standard coals, is equivalent to about the 20% of China's total energy consumption.Therefore, greatly develop biomass energy and be conducive to improving China's energy resource structure, reduce the interdependency to fossil energy simultaneously, also will become one of China important channel solving energy and environment problem.
The conversion of biomass can be divided into physical method, thermochemical study method, bioconversion method.Physical method simply changes the shape of biomass, consistency, in order to applies and stores；Thermochemical study method is, by heat chemistry, biomass conversion is prepared the materials such as carbon monoxide, hydrogen, small molecule hydrocarbon or bio-oil；And bioconversion is, by microorganism or enzyme, biomass are carried out the process of biochemical reaction.
Bio-oil is a kind of liquid containing oxygen mixture, mainly includes the oxygenatedchemicalss such as carboxylic acid, phenol and aldehyde ketone.Due to the peculiar property of bio-oil, cause it unstable, especially its thermal instability, limit its direct applied scope.Bio-oil refined relatively difficult, is different from the refined of crude oil fractions and coal liquefaction component.How to overcome biomass to have a deficiency in physical attribute, and make full use of the Technology of existing process petroleum-based energy, for producing the development path that renewable green transport fuel is a kind of sustainability.
In the bio-oil method of hydrotreating that prior art provides, do not take into full account that impurity in bio-oil raw material is on the process of by-product after the impact of hydrogenation reaction and hydrogenation, or hydrogenation reaction order is unreasonable, catalyst poisoning or inactivation may be caused, the life-span of serious curtailment hydrogenation catalyst, ultimately result in device shortening service cycle, and hydrogenation reaction efficiency is low, it is difficult to obtain the green fuel product of high-quality.
Utility model content
For the deficiencies in the prior art, this utility model provides a kind of combined hydrogenation device utilizing bio-oil to produce environmental protection transport fuel, described device is with reproducible bio-oil as raw material, use two-stage hydrogenation combined system, directly application or the green transport fuel with fossil class transport fuel blending can be obtained, flow process is simple, consumes energy low, has extremely strong practical reference value.
Specifically, this utility model provides a kind of combined hydrogenation device utilizing bio-oil to produce environmental protection transport fuel, and described device includes the bio-oil preprocessor that order is connected, one section of high-temperature hydrogenation fixed bed reactors, one section of product gas-liquid separator, two-stage nitration high-temperature hydrogenation fixed bed reactors, second-stage reaction product gas-liquid separator and atmospheric distillation tower.
In actual production, described device specifically includes bio-oil preprocessor that order is connected, hydrogenation feed pump, charging heating furnace, one section of high-temperature hydrogenation fixed bed reactors, one section of product gas-liquid separator, two-stage nitration high-temperature hydrogenation fixed bed reactors, second-stage reaction product gas-liquid separator and atmospheric distillation tower.
Described one section of high-temperature hydrogenation fixed bed reactors and two-stage nitration high-temperature hydrogenation fixed bed reactors all configure reaction feed/product exchanger；Reaction raw materials is after described reaction feed/product exchanger, entering hydrogenation fixed bed and carry out hydrogenation reaction, the product of reaction gained again passes by described reaction feed/product exchanger, carries out heat exchange between product and raw material, thus make full use of the heat in device, reduce energy consumption.
The one section of low temperature hydrogenation fixed bed reactors being adjacent can also be set before described charging heating furnace, pretreated bio-oil raw material can first carry out low temperature hydrogenation refine, carry out high-temperature hydrogenation again to refine, thus fully remove the unstable component in bio-oil, such as Organic substances such as biological colloid, macromole lipid, destabilised fat acid and biological fibers, avoid these materials coking and blocking catalyst when high-temperature hydrogenation, reduce catalyst service life, affect catalytic effect.
Each hydrogenation fixed bed reactors described in the utility model use multistage hierarchical arrangement, and its lower floor arranges loaded catalyst bed, and its upper strata is provided with inert catalyst bed and dirt retracting device.
Described atmospheric distillation tower includes liquefied gas output channel, gasoline output channel, kerosene output channel and diesel oil output channel.Described atmospheric distillation tower also includes tail oil output channel, described tail oil pipeline can be connected with bio-oil raw material preprocessing device, can also be connected with the liquid phase output of one section of product gas-liquid separator, after tail oil is mixed in proper proportions with raw material, can recycle.
Described device also includes hydrogen-feeding system.Described hydrogen-feeding system includes make-up hydrogen compressor and circulating hydrogen compressor, and the two provides reactive hydrogen and quenching hydrogen by hydrogen supply pipeline for each consumption hydrogen production device.The top of described one section of product gas-liquid separator and second-stage reaction product gas-liquid separator is gas delivery channels, it is connected with described circulating hydrogen compressor respectively through hydrogen refining plant, isolated gas phase inputting hydrogen refining plant is recycled, in hydrogen input circulating hydrogen compressor after Jing Zhi, it is achieved the cycling and reutilization of hydrogen.
This utility model is with bio-oil as raw material, described biomass main body of oil includes triglyceride and free fatty, selected from vegetable oil, animal oil, one or more in biomass pyrolysis oil, remaining meal oil, or vegetable oil, animal oil, biomass pyrolysis oil is or/and remaining meal is oily and the mixture of hydrocarbon-type oil.Described vegetable oil is preferably Oleum Gossypii semen, Oleum Helianthi, Castor oil or/and Petiolus Trachycarpi oil.Described remaining meal oil refers to the edible oil (predominantly vegetable oil or animal oil) product after culinary art uses.Described biomass pyrolysis oil refers to that various renewable raw materials is through fast pyrogenation or the oil plant obtained by thermochemical method synthesizes.
Use the device that this utility model provides, can carry out producing according to the method comprised the following steps the combined hydrogenation of green transport fuel:
(1) bio-oil raw material is carried out remove impurity pretreatment, obtain pretreatment fluid；
(2) using containing metallic nickel, cobalt or/and the loaded catalyst of molybdenum, described pretreatment fluid is carried out hydrofinishing process, product, after gas-liquid separation, collects hydrofinishing liquid phase；
(3) using the loaded catalyst containing noble metal, described hydrofinishing liquid phase is carried out hydroisomerization process, product, after gas-liquid separation, collects hydroisomerization liquid phase；
(4) described hydroisomerization liquid phase carries out air-distillation, collects the many heavy distillat including liquefied gas, gasoline, kerosene and diesel oil.
Moisture in the purpose of step (1) described pretreatment mainly abjection raw material, salt, biological colloid, alkalinous metal and other catalyst poisons, it is to avoid catalyst poisoning inactivation during downstream reaction, thus improve the efficiency of hydrogenation catalyst reaction.This utility model can select concrete preprocess method according to the character of recyclable organism raw material, can be selected for a kind of method in washing-filtration-rectification under vacuum technique, clay-filtered, ion exchange resin treatment, activated carbon adsorption or several method is shared.
This utility model preferably employs acid-exchange resin and activated carbon and described bio-oil raw material is carried out pretreatment.Specifically, acid-exchange resin, it it is the cross-linked copolymer (microsphere diameter is generally 0.5 handkerchief micron) of a kind of microspheroidal aggregation being wrapped in a jumble, it had both possessed the gelinite of ordinary gel resin, having again the unexistent macroporous structure of gel resin, this pore structure is made up of the cavity between microsphere and duct, has specific inner surface and pore diameter range, even if in the dry state, its aperture is general also between 20～2000 angstroms；Activated carbon has many capillary channels, has certain active center when high temperature simultaneously, and surface area is big, can use as adsorbent, desiccant and catalyst.Polarity power always according to adsorbent determines water, oxide, acetic acid, alkali etc. are had stronger affinity, is a kind of micro-water depth desiccant simultaneously, is also the adsorbent of absorption polar molecule.Using acid-exchange resin and activated carbon to carry out pretreatment, it can be ensured that in material liquid, water content is less than 1mg/L, sulfur content is less than 5ppm, it is also possible to reduce the content of the materials such as salt, colloid, alkali metal in raw material.
Step (2) and step (3) described hydrotreating are both needed to use load hydrogenation catalyst.Described load hydrogenation catalyst mainly includes metal active constituent and carrier；Wherein, metal active constituent is that reaction provides hydrogenation sites, and including group vib or/and group VIII metal is or/and its oxide, one or more metals in Mo, Ni, Co, W, Pd, Pt are or/and its oxide；Described carrier provides distribution carrier for active component, and selected from refractory aluminium oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., the shape of carrier can be spherical or cloverleaf pattern.
Described hydrogenation catalyst can also include auxiliary agent and inert catalyst.Described auxiliary agent, for regulating the character such as metal active constituent and the structure of carrier, character, activity, catalytic selectivity, hydrogen consumption, life-span, can be selected for P, Si, B, Ti, Zr etc..The major function of described inert catalyst is guard catalyst, removes objectionable impurities, carries out the functions such as gas-liquid distribution.
Specifically, step (2) described hydrofinishing processes the catalyst used and preferably comprises the metal active constituent of nickel, using refractory aluminium oxide or/and silicon oxide is as carrier.This utility model utilizes the function of the low-temp desulfurization denitrogenation deoxidation of nickel catalyst, heteroatomic compound, remaining metallo-organic compound, the saturated polycyclic aromatic hydrocarbons such as removing sulfur, nitrogen, oxygen, and partial hydrogenation is saturated, reduce the reaction temperature of catalyst in follow-up hydrocracking step, slow down the inactivation of hydroisomerisation catalysts, thus extend the service cycle of hydroisomerisation step catalyst.As a kind of preferred version of the present utility model, in the catalyst that step (2) uses, containing the metallic nickel that mass percent is 2～8%, carrier is refractory aluminium oxide or/and silicon oxide.
In described step (2), in order to improve the efficiency that hydrofinishing processes, the gas-liquid volume ratio preferably reacted is 500～1000:1, and liquid hourly space velocity (LHSV) is 0.5～5.0h-1, pressure is 4～15MPa, and temperature is 250～350 DEG C；Further preferably the gas-liquid volume ratio of reaction is 800～1000:1, and liquid hourly space velocity (LHSV) is 0.5～1h-1, pressure is 4.5～10MPa, and temperature is 310～350 DEG C.Under the above-described reaction conditions, removable sulfur, nitrogen, oxygen, and carry out being hydrogenated with saturated and partial hydrogenation cracking reaction, abundant reacted product is after gas-liquid separation, gas phase comprises the light-component gas virose to hygrogenating isomerization reaction catalyst such as ammonia, hydrogen sulfide, water, reusable edible after refined, the liquid phase hydroisomerization for next stage processes.
In step (2) described unifining process, when bio-oil is that biomass directly or indirectly liquefy or it mixes with fossil fuels, high-temperature hydrogenation can be directly used to refine.If bio-oil raw material is vegetable oil, animal oil or remaining meal oil, owing to the gum level in these a few biolobic material oil raw materials is higher, in order to fully remove the unstable component in bio-oil, such as Organic substances such as biological colloid, macromole lipid, destabilised fat acid and biological fibers, avoid these materials coking and blocking catalyst when high-temperature hydrogenation, reduce catalyst service life, affect catalytic effect, the colloid in first low temperature pre-hydrogenation and removing bio-oil and partial hydrogenation can be used, carry out the method that high-temperature hydrogenation is refined again.
Specifically, step (2) can first carry out low temperature hydrogenation refinement treatment, then carries out high-temperature hydrogenation refinement treatment.Described step (2) can first 2～8MPa, 120～250 DEG C, gas-liquid volume ratio 500～1000:1, liquid hourly space velocity (LHSV) be 0.5～5.0h-1Under conditions of described pretreatment fluid carried out low temperature hydrogenation refinement treatment, then 4～15MPa, 250～350 DEG C, gas-liquid volume ratio 800～1000:1, liquid hourly space velocity (LHSV) be 0.5～1h-1Under conditions of carry out high-temperature hydrogenation refinement treatment.Preferably, described step (2) can first 2～8MPa, 120～250 DEG C, gas-liquid volume ratio 800～1000:1, liquid hourly space velocity (LHSV) be 0.5～1h-1Under conditions of described pretreatment fluid carried out low temperature hydrogenation refinement treatment, then 4.5～10MPa, 310～350 DEG C, gas-liquid volume ratio 800～1000:1, liquid hourly space velocity (LHSV) be 0.5～1h-1Under conditions of carry out high-temperature hydrogenation refinement treatment.
Step (2) utilizes nickel catalyst to carry out effective HDM, desulfurization, denitrogenation, deoxidation, wherein deoxidation mainly includes the reactions such as decarboxylation, decarbonylation base and hydrogenation deoxidation, triglyceride in bio-oil changes into linear paraffin compounds, and Removal of catalyst poisonous substance provides the condition of long period operation for secondary hydrogenation；Linear paraffin component can also be obtained by appropriateness hydrogenation simultaneously.
The main purpose that step (3) described hydroisomerization processes is that linear paraffin is changed into branched paraffin, the hydrogenation catalyst that this step uses is preferably loaded noble metal catalyst, belong to bifunctional catalyst, there is the strongest cracking, de-virtue, isomery and lighting activity, it can be ensured that cracking and isomerization reaction are thoroughly carried out.
Described loaded noble metal catalyst includes the noble metal component providing hydrogenation/dehydrogenation function and provides the acid carrier of cracking function；Wherein, described noble metal component can be selected for Pt or Pd, and described acid carrier can be selected for molecular sieve, amorphous silicon aluminium, unformed silicon magnesium, modified aluminas, SAPO-11, SAPO-31, ZSM-22, ZSM-35 etc..As a kind of preferred version of the present utility model, in the hydrogenation catalyst that step (3) uses, containing 2～the precious metal palladium of 8%, carrier is Si-Al zeolite or/and molecular sieve.
In described step (3), in order to improve the efficiency of hydroisomerization, the pressure preferably reacted is 4～15MPa, and temperature is 330～420 DEG C, and hydrogen to oil volume ratio is 600～1000:1, and liquid hourly space velocity (LHSV) is 0.5～5.0h-1；Further preferably hydrogenation pressure is 4.5～10MPa, and temperature is 350～380 DEG C, and hydrogen to oil volume ratio is 700～1000:1, and liquid hourly space velocity (LHSV) is 1～3h-1。
This utility model is by carrying out the most preferably to the hydrogenation catalyst used in step (2) and step (3) and reaction condition, ensure that the activity of hydrogenation catalyst, avoid constantly depositing because of impurity with quick coking covering catalyst active center and cause the minimum economic cycle of operation that the operation cycle is the shortest, be difficult to maintain course of industrialization requirement, ensure that the degree of depth and the effect of catalytic hydrogenation reaction simultaneously.
Step (2) and step (3) are required to product is carried out gas-liquid separation; the catalyst poison such as hydrogen sulfide, ammonia and moisture that hydrogenation reaction produces can be removed; the hydrogenation activity making catalyst is protected; the hydroisomerization of material is thorough, it is ensured that the product of acquisition, especially diesel oil distillate have preferable low temperature flowability；Meanwhile, unreacted hydrogen is reclaimed by flash distillation means.
Step (4) uses traditional air-distillation to carry out precision fractionation, corresponding target product fraction is extracted out at the different parts of atmospheric distillation tower according to the boiling point of each fraction, tower top is liquefied gas, and middle part extracts gasoline fraction, kerosene distillate, diesel oil distillate successively out, is tail oil at the bottom of tower.After described tail oil is mixed in suitable ratio with bio-oil raw material, can use as feedstock circulation.After the method provided according to this utility model is combined hydrogenation, low freezing point diesel fuel fraction, kerosene distillate and the gasoline fraction that step (4) obtains can directly be applied or transport fuel with the green of fossil class transport fuel blending.
Form when described bio-oil is directly or indirectly liquefied by biomass, or the product directly or indirectly liquefied by biomass is when mixing with fossil fuels, device described in the utility model does not include one section of low temperature hydrogenation fixed bed reactors, can carry out producing the combined hydrogenation of green transport fuel in accordance with the following methods:
(1) utilize acid-exchange resin and activated carbon that bio-oil raw material is carried out remove impurity pretreatment；Obtain water content less than 1mg/L, the sulfur content pretreatment fluid less than 5ppm；
(2) using containing 2～8% metallic nickel, carrier is refractory aluminium oxide or/and the loaded catalyst of silicon oxide, 4.5～10MPa, 310～350 DEG C, gas-liquid volume ratio 800～1000:1, liquid hourly space velocity (LHSV) 0.5～1h-1Under conditions of, described pretreatment fluid is carried out hydrofinishing process, product, after gas-liquid separation, collects hydrofinishing liquid phase；
(3) using containing 2～5% Metal Palladium, carrier is Si-Al zeolite or/and the loaded catalyst of molecular sieve, 4.5～10MPa, 350～380 DEG C, gas-liquid volume ratio 700～1000:1, liquid hourly space velocity (LHSV) 1～3h-1Under conditions of, described hydrofinishing liquid phase is carried out hydroisomerization process, product, after gas-liquid separation, collects hydroisomerization liquid phase；
(4) described hydroisomerization liquid phase carries out air-distillation, collects the many heavy distillat including liquefied gas, gasoline, kerosene and low freezing point diesel fuel.
When described bio-oil is vegetable oil, animal oil or remaining meal oil, device described in the utility model includes one section of low temperature hydrogenation fixed bed reactors, can carry out producing the combined hydrogenation of green transport fuel in accordance with the following methods:
(1) utilize acid-exchange resin and activated carbon that bio-oil raw material is carried out remove impurity pretreatment；Obtain water content less than 1mg/L, the sulfur content pretreatment fluid less than 5ppm；
(2) using containing 2～8% metallic nickel, carrier is refractory aluminium oxide or/and the loaded catalyst of silicon oxide, first 2～8MPa, 120～250 DEG C, gas-liquid volume ratio 800～1000:1, liquid hourly space velocity (LHSV) be 0.5～1h-1Under conditions of described pretreatment fluid carried out low temperature hydrogenation refinement treatment, then 4.5～10MPa, 310～350 DEG C, gas-liquid volume ratio 800～1000:1, liquid hourly space velocity (LHSV) be 0.5～1h-1Under conditions of carry out high-temperature hydrogenation refinement treatment, product after gas-liquid separation, collect hydrofinishing liquid phase；
(3) using containing 2～5% Metal Palladium, carrier is Si-Al zeolite or/and the loaded catalyst of molecular sieve, 4.5～10MPa, 350～380 DEG C, gas-liquid volume ratio 700～1000:1, liquid hourly space velocity (LHSV) 1～3h-1Under conditions of, described hydrofinishing liquid phase is carried out hydroisomerization process, product, after gas-liquid separation, collects hydroisomerization liquid phase；
(4) described hydroisomerization liquid phase carries out air-distillation, collects the many heavy distillat including liquefied gas, gasoline, kerosene and low freezing point diesel fuel.
Use device described in the utility model to produce the fraction obtained and there is good combination property, wherein, the Cetane number of low freezing point diesel fuel fraction can reach more than 60, there is preferable cryogenic property, its condensation point is lower 5～15 DEG C than-No. 10 conventional condensation point of diesel oil, can be applied to commercial production and transport field as green fuel.
The device that this utility model provides is with reproducible bio-oil as raw material, use two-stage hydrogenation combined system, by catalyst, the reaction mechanism mechanism of reaction and reaction condition are optimized, directly application or the green transport fuel with fossil class transport fuel blending can be obtained, flow process is simple, consume energy low, there is extremely strong practical reference value.
Accompanying drawing explanation
Fig. 1 is combined hydrogenation device schematic diagram described in embodiment 1,2；Wherein: 1 is bio-oil pretreatment unit, 2 is make-up hydrogen compressor, 3 is hydrogenation feed pump, 4 is one section of reaction feed/product exchanger, 5 is charging heating furnace, 6 is circulating hydrogen compressor, 7 is one section of high-temperature hydrogenation fixed bed reactors, 8 is one section of product gas-liquid separator, and 9 is second-stage reaction charging/product exchanger, and 10 is two-stage nitration high-temperature hydrogenation fixed bed reactors, 11 is second-stage reaction product gas-liquid separator, 12 is atmospheric distillation tower, and 13 is hydrogen refining plant, and 14 is one section of low temperature hydrogenation fixed bed reactors.
Detailed description of the invention
Following example are used for illustrating this utility model, but are not limited to scope of the present utility model.
Embodiment 1
Present embodiments provide a kind of combined hydrogenation device utilizing bio-oil to produce environmental protection transport fuel, with reference to shown in Fig. 1, including the bio-oil preprocessor 1 being sequentially connected, hydrogenation feed pump 3, charging heating furnace 7, one section of product gas-liquid separator 8 of 5, one section of high-temperature hydrogenation fixed bed reactors, two-stage nitration high-temperature hydrogenation fixed bed reactors 10, second-stage reaction product gas-liquid separator 11, atmospheric distillation tower 12；
Described one section of high-temperature hydrogenation fixed bed reactors 7 are equipped with one section of reaction feed/product exchanger 4；After the hydrogenated feed pump of raw material 3, sequentially enter one section of reaction feed/product exchanger 4, charging heating furnace 5 and one section of high-temperature hydrogenation fixed bed reactors 7, it is again introduced into described one section of reaction feed/product exchanger 4 from one section of product of one section of high-temperature hydrogenation fixed bed reactors 7 output, between product and reaction raw materials, carries out heat exchange；One section of product through described heat exchange enters one section of product gas-liquid separator 8；
Described two-stage nitration high-temperature hydrogenation fixed bed reactors 10 are equipped with second-stage reaction charging/product exchanger 9；Raw material is after one section of product gas-liquid separator 8, sequentially enter second-stage reaction charging/product exchanger 9 and two-stage nitration high-temperature hydrogenation fixed bed reactors 10, it is again introduced into described second-stage reaction charging/product exchanger 9 from the second-stage reaction product of two-stage nitration high-temperature hydrogenation fixed bed reactors 10 output, between product and reaction raw materials, carries out heat exchange；Second-stage reaction product through described heat exchange enters second-stage reaction product gas-liquid separator 11；
Make-up hydrogen compressor 2, circulating hydrogen compressor 6 provide reactive hydrogen and quenching hydrogen by Hydrogen Line for each consumption hydrogen production device；
One section of product gas-liquid separator 8 is connected with circulating hydrogen compressor 6 respectively through hydrogen refining plant 13 with second-stage reaction product gas-liquid separator 11, it is achieved the recycling of hydrogen.
In described device, participate in hydrogenation process high-temperature hydro-refining pipeline use chrome-molybdenum steel high-temperature resistant pipeline, in non-hydrogen, cryogenic piping use ordinary carbon steel pipeline.
Embodiment 2
Present embodiments provide a kind of combined hydrogenation device utilizing bio-oil to produce environmental protection transport fuel, as it is shown in figure 1, include the bio-oil preprocessor 1 being sequentially connected, hydrogenation 3, one section of low temperature hydrogenation fixed bed reactors 14 of feed pump, feed heating furnace 7, one section of product gas-liquid separator 8 of 5, one section of high-temperature hydrogenation fixed bed reactors, two-stage nitration high-temperature hydrogenation fixed bed reactors 10, second-stage reaction product gas-liquid separator 11, atmospheric distillation tower 12；
Described one section of high-temperature hydrogenation fixed bed reactors 7 are equipped with one section of reaction feed/product exchanger 4；After the hydrogenated feed pump of raw material 3, sequentially enter 4, one section of low temperature hydrogenation fixed bed reactors 14 of one section of reaction feed/product exchanger, charging heating furnace 5 and one section of high-temperature hydrogenation fixed bed reactors 7, it is again introduced into described one section of reaction feed/product exchanger 4 from one section of product of one section of high-temperature hydrogenation fixed bed reactors 7 output, between product and reaction raw materials, carries out heat exchange；One section of product through described heat exchange enters one section of product gas-liquid separator 8；
Described two-stage nitration high-temperature hydrogenation fixed bed reactors 10 are equipped with second-stage reaction charging/product exchanger 9；Raw material is after one section of product gas-liquid separator 8, sequentially enter second-stage reaction charging/product exchanger 9 and two-stage nitration high-temperature hydrogenation fixed bed reactors 10, it is again introduced into described second-stage reaction charging/product exchanger 9 from the second-stage reaction product of two-stage nitration high-temperature hydrogenation fixed bed reactors 10 output, between product and reaction raw materials, carries out heat exchange；Second-stage reaction product through described heat exchange enters second-stage reaction product gas-liquid separator 11；
Make-up hydrogen compressor 2, circulating hydrogen compressor 6 provide reactive hydrogen and quenching hydrogen by Hydrogen Line for each consumption hydrogen production device；
One section of product gas-liquid separator 8 is connected with circulating hydrogen compressor 6 respectively through hydrogen refining plant 13 with second-stage reaction product gas-liquid separator 11, it is achieved the recycling of hydrogen.
In described device, participate in hydrogenation process high-temperature hydro-refining pipeline use chrome-molybdenum steel high-temperature resistant pipeline, in non-hydrogen, cryogenic piping use ordinary carbon steel pipeline.
Embodiment 3
Use the device that embodiment 1 provides, with the oil plant of biomass fast pyrogenation gained as raw material, be combined hydrogenation in accordance with the following methods:
(1) utilize acid cation exchange resin and the ball shape active carbon with φ 5～φ 20 classification filling, Oleum Gossypii semen raw material is carried out remove impurity pretreatment；Obtain the pretreatment fluid that water content is less than 0.1% less than 1mg/L, sulfur content less than 5ppm, gum level less than 1mg/L, salt content；
(2) use containing cloverleaf pattern loaded catalyst that 5% metallic nickel, carrier are refractory aluminium oxide and silicon oxide (high holding sulfur low nickel catalytic hydrogenation purchased from Fushun petrochemical industry is graduate), using large-pore alumina active porcelain ball as inert catalyst, 8MPa, 320 DEG C, gas-liquid volume ratio 1000:1, liquid hourly space velocity (LHSV) 0.5h-1Under conditions of, described pretreatment fluid is carried out direct high-temperature hydrogenation refinement treatment, product, after gas-liquid separation, collects hydrofinishing liquid phase；
(3) use containing cloverleaf pattern loaded catalyst that 5% Metal Palladium, carrier are Si-Al zeolite and molecular sieve (purchased from Chinese Academy of Sciences's Shanxi coalification palladium metal Hydrobon catalyst), using large-pore alumina active porcelain ball as inert catalyst, 10MPa, 360 DEG C, gas-liquid volume ratio 1000:1, liquid hourly space velocity (LHSV) 1.5h-1Under conditions of, described hydrofinishing liquid phase is carried out hydroisomerization process, product, after gas-liquid separation, collects hydroisomerization liquid phase；
(4) described hydroisomerization liquid phase carries out air-distillation, collects the many heavy distillat including liquefied gas, gasoline, kerosene and diesel oil.
After testing, the condensation point of step (4) gained diesel oil is substantially less than-No. 10 conventional diesel oil.
Embodiment 4
Use the device that embodiment 2 provides, with Oleum Gossypii semen as raw material, be combined in accordance with the following methods being hydrogenated with:
(1) utilize acid cation exchange resin and the ball shape active carbon with φ 5～φ 20 classification filling, Oleum Gossypii semen raw material is carried out remove impurity pretreatment；Obtain the pretreatment fluid that water content is less than 0.1% less than 1mg/L, sulfur content less than 5ppm, gum level less than 1mg/L, salt content；
(2) use containing cloverleaf pattern loaded catalyst that 5% metallic nickel, carrier are refractory aluminium oxide and silicon oxide (high holding sulfur low nickel catalytic hydrogenation purchased from Fushun petrochemical industry is graduate), using large-pore alumina active porcelain ball as inert catalyst, first 8MPa, 180 DEG C, gas-liquid volume ratio 1000:1, liquid hourly space velocity (LHSV) be 0.5h-1Under conditions of described pretreatment fluid carried out low temperature hydrogenation refinement treatment, then 8MPa, 320 DEG C, gas-liquid volume ratio 1000:1, liquid hourly space velocity (LHSV) 0.5h-1Under conditions of carry out high-temperature hydrogenation refinement treatment, product after gas-liquid separation, collect hydrofinishing liquid phase；
(3) use containing cloverleaf pattern loaded catalyst that 5% Metal Palladium, carrier are Si-Al zeolite and molecular sieve (purchased from Chinese Academy of Sciences's Shanxi coalification palladium metal Hydrobon catalyst), using large-pore alumina active porcelain ball as inert catalyst, 10MPa, 360 DEG C, gas-liquid volume ratio 1000:1, liquid hourly space velocity (LHSV) 1.5h-1Under conditions of, described hydrofinishing liquid phase is carried out hydroisomerization process, product, after gas-liquid separation, collects hydroisomerization liquid phase；
(4) described hydroisomerization liquid phase carries out air-distillation, collects the many heavy distillat including liquefied gas, gasoline, kerosene and diesel oil.
After testing, the condensation point of step (4) gained diesel oil is substantially less than-No. 10 conventional diesel oil.
Although, to use general explanation, detailed description of the invention and test, this utility model has been made detailed description, but on the basis of this utility model, it can have been made some modifications or improvements, this will be apparent to those skilled in the art.Therefore, these modifications or improvements on the basis of without departing from this utility model spirit, belong to the scope that this utility model is claimed.
Claims (10)
1. one kind utilizes the combined hydrogenation device that bio-oil produces environmental protection transport fuel, it is characterized in that, the bio-oil preprocessor being connected including order, one section of high-temperature hydrogenation fixed bed reactors, one section of product gas-liquid separator, two-stage nitration high-temperature hydrogenation fixed bed reactors, second-stage reaction product gas-liquid separator and atmospheric distillation tower；Described device also includes hydrogen-feeding system.
Device the most according to claim 1, it is characterised in that one section of low temperature hydrogenation fixed bed reactors is set between described bio-oil preprocessor and one section of high-temperature hydrogenation fixed bed reactors.
Device the most according to claim 1 and 2, it is characterised in that before described one section of high-temperature hydrogenation fixed bed reactors, the charging heating furnace being adjacent is set.
Device the most according to claim 1 and 2, it is characterised in that described one section of high-temperature hydrogenation fixed bed reactors and two-stage nitration high-temperature hydrogenation fixed bed reactors all configure reaction feed/product exchanger；Reaction raw materials, after described reaction feed/product exchanger, enters hydrogenation fixed bed reactors and carries out hydrogenation reaction, and gained product again passes by described reaction feed/product exchanger, carries out heat exchange between product and reaction raw materials.
Device the most according to claim 1, it is characterized in that, including the bio-oil preprocessor being sequentially connected, hydrogenation feed pump, charging heating furnace, one section of high-temperature hydrogenation fixed bed reactors, one section of product gas-liquid separator, two-stage nitration high-temperature hydrogenation fixed bed reactors, second-stage reaction product gas-liquid separator, atmospheric distillation tower；
Described one section of high-temperature hydrogenation fixed bed reactors are equipped with one section of reaction feed/product exchanger；After the hydrogenated feed pump of raw material, sequentially enter one section of reaction feed/product exchanger, charging heating furnace and one section of high-temperature hydrogenation fixed bed reactors, it is again introduced into described one section of reaction feed/product exchanger from one section of product of one section of high-temperature hydrogenation fixed bed reactors output, between product and reaction raw materials, carries out heat exchange；One section of product through described heat exchange enters one section of product gas-liquid separator；
Described two-stage nitration high-temperature hydrogenation fixed bed reactors are equipped with second-stage reaction charging/product exchanger；Raw material is after one section of product gas-liquid separator, sequentially enter second-stage reaction charging/product exchanger and two-stage nitration high-temperature hydrogenation fixed bed reactors, it is again introduced into described second-stage reaction charging/product exchanger from the second-stage reaction product of two-stage nitration high-temperature hydrogenation fixed bed reactors output, between product and reaction raw materials, carries out heat exchange；Second-stage reaction product through described heat exchange enters second-stage reaction product gas-liquid separator.
Device the most according to claim 1, it is characterized in that, including the bio-oil preprocessor being sequentially connected, hydrogenation feed pump, one section of low temperature hydrogenation fixed bed reactors, charging heating furnace, one section of high-temperature hydrogenation fixed bed reactors, one section of product gas-liquid separator, two-stage nitration high-temperature hydrogenation fixed bed reactors, second-stage reaction product gas-liquid separator, atmospheric distillation tower；
Described one section of high-temperature hydrogenation fixed bed reactors are equipped with one section of reaction feed/product exchanger；After the hydrogenated feed pump of raw material, sequentially enter one section of reaction feed/product exchanger, one section of low temperature hydrogenation fixed bed reactors, charging heating furnace and one section of high-temperature hydrogenation fixed bed reactors, it is again introduced into described one section of reaction feed/product exchanger from one section of product of one section of high-temperature hydrogenation fixed bed reactors output, between product and reaction raw materials, carries out heat exchange；One section of product through described heat exchange enters one section of product gas-liquid separator；
Described two-stage nitration high-temperature hydrogenation fixed bed reactors are equipped with second-stage reaction charging/product exchanger；Raw material is after one section of product gas-liquid separator, sequentially enter second-stage reaction charging/product exchanger and two-stage nitration high-temperature hydrogenation fixed bed reactors, it is again introduced into described second-stage reaction charging/product exchanger from the second-stage reaction product of two-stage nitration high-temperature hydrogenation fixed bed reactors output, between product and reaction raw materials, carries out heat exchange；Second-stage reaction product through described heat exchange enters second-stage reaction product gas-liquid separator.
7. according to the device described in claim 1,2,5 or 6, it is characterised in that described one-stage hydrogenation fixed bed reactors and secondary hydrogenation fixed bed reactors all use layered configuration；
The lower floor of described reactor arranges loaded catalyst bed, and the upper strata of described reactor is provided with inert catalyst bed and dirt retracting device.
8. according to the device described in claim 1,2,5 or 6, it is characterised in that described hydrogen-feeding system includes make-up hydrogen compressor and circulating hydrogen compressor；
Described one section of product gas-liquid separator is connected with described circulating hydrogen compressor respectively through hydrogen refining plant with second-stage reaction product gas-liquid separator.
9. according to the device described in claim 1,2,5 or 6, it is characterised in that described atmospheric distillation tower includes liquefied gas output channel, gasoline output channel, kerosene output channel, diesel oil output channel.
Device the most according to claim 9, it is characterised in that described air-distillation also tower includes tail oil output channel；
Described tail oil pipeline is connected with bio-oil raw material preprocessing device, or is connected with the liquid phase output of one section of product gas-liquid separator.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
| CN113293024A (en) * | 2020-04-26 | 2021-08-24 | 江西尊创新能源有限公司 | Method for preparing biodiesel by three-stage selective hydrodeoxygenation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419867A (en) * | 2015-12-30 | 2016-03-23 | 胡平 | Combined hydrogenation method and apparatus utilizing biomass oil to produce green and environment-friendly transportation fuel |
| CN113293024A (en) * | 2020-04-26 | 2021-08-24 | 江西尊创新能源有限公司 | Method for preparing biodiesel by three-stage selective hydrodeoxygenation |
| CN113293024B (en) * | 2020-04-26 | 2023-05-26 | 江西尊创新能源有限公司 | Method for preparing biodiesel by three-stage selective hydrodeoxygenation |
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