CN102029174A - Catalyst for producing fuel oil - Google Patents
Catalyst for producing fuel oil Download PDFInfo
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- CN102029174A CN102029174A CN 201010563660 CN201010563660A CN102029174A CN 102029174 A CN102029174 A CN 102029174A CN 201010563660 CN201010563660 CN 201010563660 CN 201010563660 A CN201010563660 A CN 201010563660A CN 102029174 A CN102029174 A CN 102029174A
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Abstract
The invention discloses a catalyst for producing fuel oil, comprising a carrier and an active component. The catalyst is characterized in that the active component is a brominated compound, and the carrier has a molecular sieve. When the provided catalyst for producing fuel oil is used for producing fuel oil, coal tar hydrogenation modification is not needed, a technical process for preparing fuel oil by using coal tar is simple, a production technology is easy to master, and the equipment investment is low. Compared with the prior art for preparing fuel oil by using coal tar, the fuel oil prepared by using the catalyst provided by the invention has high yield, and moreover, the color of the prepared coarse fuel oil can not darken when stored for a long period. A test shows that when the coal tar is used for preparing the fuel oil by using the catalyst, the yield of the fuel oil is over 64 percent.
Description
Technical field
The invention belongs to the Preparation of Catalyst field, particularly coal tar prepares fuel oil catalyst aspect.
Background technology
How to effectively utilize coal resources and make it meet the research direction that environmental protection requirement is various countries always.Coal tar is one of product of the dry distillation of coal and coal generating gas.In China, the deep processing of coal tar once received much attention and dropped into substantial contribution and manpower is studied in twentieth century 50, the sixties.Because oil has been found on ground such as grand celebration, Liaoning, Shandong, Henan, Xinjiang, from twentieth century 60, the seventies, the research and development that China produces high-quality environment-friendly liquid product to coal tar deep processing almost stagnate.Up to twentieth century end of the nineties, along with the consumption day by day of petroleum resources in the world wide and the increase year by year of domestic imported crude oil ratio, how rationally to utilize the substitute of this oil of coal tar to be subjected to increasing attention with fuel oil and other industrial chemicals that obtains high-quality.
At present, the required coke major part of domestic steel-making enterprise is from coal, and process of coking can generate accessory substance coal tar.There is gasification plant production city coal gas in domestic many cities, and coal tar also is byproduct, and coal tar output is more at the gasification plant below 50,000 tons/year.In recent years, market increases year by year to the demand of fuel oil, in, coalite tar has the characteristic of natural crude oil, but compare with ordinary crude oils and to have that density is big, viscosity is high, sulfur content is high, especially the H/C mol ratio is low, nitrogen content is high, carbon residue and asphalitine height, therefore second-rate, relatively be difficult to processing.Along with the year by year increase of market to the fuel oil demand, a kind of economic means that coal tar is processed into fuel oil is being sought by domestic a lot of coal tar processing enterprise.
At present, roughly there are three kinds of approach in China coal tar processing enterprise to the coal tar oil treatment process: first kind of approach, coal tar cuts various cuts such as light oil, carbolic oil, naphtalene oil, washing oil and carbolineum through atmospheric and vacuum distillation, the single-component product that desires such as phenol, naphthalene, anthracene are extracted is concentrated in the corresponding cut, further utilize physics to separate again, obtain high value added products such as naphthalene, phenol, anthracene, phenanthrene, carbazole, pitch with chemical method.This class processing method technological process complexity, scale of investment are big, to high technology content, change direction on a large scale and develop.
Second kind of approach, coal tar be through after the air-distillation, distillate through acid-alkali refining as the low-quality fuel oil burning that directly acts as a fuel after burning or the emulsification.Meanwhile, wherein contained sulphur, nitrogen impurity become SO in combustion process
x, NO
x, and the acid-alkali refining process has produced a large amount of acid sludges, alkaline residue and sewage, not only deficiency in economic performance, and contaminated environment.CN1064882A discloses a kind of method that adopts distillation to add acid-alkali washing production fuel oil.The whole world is being faced with great ecological environment problem, and China's ecological environment also faces with industrial development the present situation that worsens day by day, is generally paying attention under the prerequisite of environmental protection at present, and this coal tar processing approach has been difficult to better development.
Article three, approach is a feedstock oil with coal tar, adopts suitable hydrofinishing process production clean fuel or the oil product suitable with oil product, not only has remarkable economic efficiency, and obvious social is also arranged simultaneously.CN1464031A, CN1772846A, CN1147575C; US4855037 discloses a kind of coal tar hydrogenation modification technology and catalyst; its technology characteristics is generally to take the catalyst filling scheme of two sections gratings, top dress protective agent, and the bottom is a Hydrobon catalyst.Perhaps take the catalyst filling scheme of three sections gratings, top is protective agent, and the centre is a Hydrobon catalyst, and foot is a dearomatization catalyst, and its core is exactly a hydrogenation catalyst.
Compare with oil secondary operations distillate hydrogenation, the key issue that catalyst for coal tar hydrogenation modification need solve is: the one, and oxygen content height in the coal tar, the water that produces in the course of reaction can all produce adverse influence to activity, hydrothermal stability and the intensity of hydrogenation catalyst; The 2nd, colloid, carbon residue content height impel catalyst carbon deposit easily in the coal tar, easily cause the rapid deactivation of catalyst; The 3rd, sulphur, nitrogen content height in the coal tar must carry out advanced nitrogen, otherwise can influence the stability of fuel oil; The 4th, contain a large amount of aromatic hydrocarbons in the coal tar, must carry out deeply hydrodearomatizedly, and under the prerequisite that as far as possible reduces chain rupture, make aromatic hydrocarbons saturated to greatest extent, the Cetane number of fuel oil is improved.The existence of these problems makes coal tar hydrogenation catalyst compare with the catalytic hydrogenation catalyst of catalytic cracking raw fuel stock, and coal tar hydrogenation catalyst more is difficult to realize industrialization.
Therefore, the coal tar hydrogenation catalyst of present exploitation, generally with aluminium oxide, silica, the amorphous aluminum silicide of porous, titanium oxide is a carrier with molecular sieve, zeolite with appropriate acid, adds other W, Mo, Ni, F, Co isoreactivity component.This class catalyst can remove sulfur impurity, nitrogen, colloid and the asphalitine etc. in the coal tar fraction effectively.But this class catalyst is owing to contain precious metal elements such as W, Mo, and the price of catalyst is very expensive, and the cost of investment of hydrogenation technique is very high simultaneously.Under the situation that the coal tar price progressively goes up, fuel oil yield is lower and the product oil price is also not high at present, middle-size and small-size oil plant generally is difficult to adopt such catalyst owing to be difficult to recoup capital outlay.
Summary of the invention
The purpose of this invention is to provide coal tar and prepare fuel oil catalyst and production method thereof.The problem that solves is that existing catalyst efficiency is not high, the problem that specific aim is not strong.
For achieving the above object, the present inventor has carried out a large amount of research and performing creative labour on the basis of existing technology, developed a kind of catalyst that is used to produce fuel oil, described catalyst comprises carrier and active component, described active component is a bromine-containing compound, and described carrier is the carrier that contains molecular sieve.With the catalyst weight is benchmark, and bromine-containing compound is preferably 0.8-3% with the 0.3-10% that Br counts catalyst weight; Described bromine-containing compound is a soluble compound, is preferably KBr, NaBr, KBrO
3Or NaBrO
3In a kind of or wherein several mixture.
Described carrier is the mixture of aluminium oxide and/or silica and molecular sieve, and described aluminium oxide is γ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3, δ-Al
2O
3And χ-Al
2O
3In one or more; Aluminium oxide is a modified aluminas, and modifier is a kind of or wherein several mixture in titanium, phosphorus, magnesium, boron, zirconium, thorium, niobium and the rare earth.Described aluminium oxide is preferably γ-Al
2O
3Or contain one or more and be selected from titanium, phosphorus, magnesium, boron, zirconium, thorium, niobium and rare earth modified γ-Al
2O
3Described aluminium oxide can be that commercially available commodity also can be by any one method preparation in the prior art, for example, can be after roasting, to make by one or more the mixture that is selected among hibbsite, monohydrate alumina and the amorphous hydroted alumina.
Described molecular screening can be a kind of or wherein several mixture in Y zeolite, beta-molecular sieve, modenite, ZRP type molecular sieve, ZSM-n type molecular sieve, SAPO-n type molecular sieve, the MCM-n type molecular sieve from the zeolite molecular sieve and/or the non-zeolite molecular sieve of Chang Zuowei catalytic cracking activity component.Most preferred molecular sieve is one or more a mixture in wherein the Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO-n type molecular sieve.Described molecular sieve can be commercially available commodity, also can adopt any one prior art for preparing.
Described catalyst to the introducing method of bromine without limits, preferable methods is that carrier was flooded 0.5-4 hour in the solution of bromine-containing compound, take out, drying, promptly.The aqueous solution of the preferred bromine-containing compound of solution of described bromine-containing compound.Described drying can adopt conventional drying means, and being preferably in temperature is under the 100-150 ℃ of condition dry 1-12 hour, and being preferably in temperature is under the 110-130 ℃ of condition dry 2-6 hour.Catalyst according to this method preparation does not need roasting process.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil, described method comprises the steps:
In reactor, add coal tar and catalyst, described catalyst is the 0.5-4% of coal tar weight, after reactor is airtight, temperature of reactor is heated to 320-400 ℃, be preferably 350-360 ℃, constant temperature 0-20 minute, be preferably 5-15 minute, product is taken out from reactor after reducing to room temperature, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil, the moisture content of described coal tar is 0-2wt%.
Utilize above-mentioned catalyst to advance the method that continuous coal tar prepares fuel oil, described method comprises the steps:
Coal tar and mixture of catalysts are imported in the reactor continuously, be preheating to 105-130 ℃ after the dehydration, coal tar after the dehydration and mixture of catalysts stop in reactor carried out catalytic reaction in 5-60 minute, the outlet temperature of product is 320-380 ℃;
Carry out separated after product derives again from reactor, get 80-280 ℃ cut, promptly get fuel oil.
Described reactor is preferably tube furnace, and the method that continuous coal tar prepares fuel oil specifically comprises the steps:
Coal tar and mixture of catalysts are imported in one section in the tube furnace continuously, described catalyst is the 0.5-4% of coal tar weight, enter one section evaporimeter dehydration after being heated to 105-130 ℃, coal tar after the dehydration and mixture of catalysts stop the 5-60 branch in two sections in tube furnace and carry out catalytic reaction, be preferably stop 10-30 minute, the outlet temperature of product is 330-370 ℃;
Product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil, and the moisture content of described coal tar is 0-2wt%.
Tube furnace used in the present invention is industrial common equipment, the permanent good fortune Zhang Dexiang of its structural representation and related description water breakthrough Zhang Chaoqun work, and coal tar separates with refining, Chemical Industry Press, 2007:53-59.
The catalyst that is used to produce fuel oil provided by the invention need not carry out coal tar hydrogenation modification when producing fuel oil, the technical process that coal tar prepares fuel oil is simple, and production technology is easy to grasp, and equipment investment is little.Compare with existing producing fuel oil from coal tar technology, utilize the fuel oil yield height of Preparation of Catalyst provided by the invention, and the raw fuel stock that makes is placed not blackening of color for a long time.Simultaneously, because high boiling cut reduces in the oil product that makes, the further deep processing of raw fuel stock is easier to be carried out.Experiment shows, utilizes catalyst provided by the invention when coal tar prepares fuel oil, and the fuel oil yield is all more than 64%.
The specific embodiment
The present invention is further illustrated below in conjunction with embodiment.
The physical function parameter of the employed feedstock oil coal tar of embodiment 1-14 is: density 1005kg/m
3, carbon residue 1.2wt%, 27 ℃ of condensation points, it is 150/240,50%/90% to be 325/410 that the beginning in the boiling range is heated up in a steamer an IBP/10%, end point of distillation FBP is 512 ℃.
Employed modified aluminas and molecular sieve are all buied from market.
Embodiment 1
Catalytic component: Y zeolite 50g contains KBr 0.8g aqueous solution 30ml;
The preparation method: with the aqueous solution dipping of KBr 2 hours, is 120 ℃ conditions under dry 2 hour in temperature with Y zeolite (Wuxi City honor get profit molecular sieve factory produce), obtains catalyst, and its character sees Table 1;
KBr is counted 1.21% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 1wt%, and then adding 4.5g catalyst, after autoclave is airtight, the heating reactor makes it temperature and is elevated to 350 ℃, constant temperature 5 minutes takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 1.5% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 1wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 120-130 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 15 minutes, and the outlet temperature of product is 350-355 ℃, and product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 1.5% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 2
Catalytic component: ZSM-5 molecular sieve 50g contains KBr 0.8g aqueous solution 25ml;
The preparation method: with the aqueous solution of KBr dipping 2 hours, is 120 ℃ conditions under dry 2 hour in temperature with ZSM-5 molecular sieve (production of Zichuan, Zibo City phoenix Fine Chemical Co., Ltd), obtains catalyst, and its character sees Table 1;
KBr is counted 1.21% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 0.1wt%, and then adding 4.5g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 360 ℃, constant temperature 10 minutes takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 1.5% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 0.1wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 105-115 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 60 minutes, the outlet temperature of product is 320-330 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 1.5% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 3
Catalytic component: γ-Al
2O
350g contains KBr 1.0g aqueous solution 30ml;
Preparation method: with γ-Al
2O
3With the aqueous solution of KBr dipping 2 hours, be under 120 ℃ of conditions dry 1 hour in temperature, obtain catalyst, its character sees Table 1;
KBr is counted 1.66% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 1.8wt%, and then adding 4.5g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 350 ℃, constant temperature 15 minutes takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 1.5% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 1.8wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 110-120 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 5 minutes, the outlet temperature of product is 360-380 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 1.5% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 4
Catalytic component: the γ-A1 of titanium modification
2O
350g contains sodium bromide 0.3g aqueous solution 30ml;
Preparation method: with the γ-Al of titanium modification
2O
3(production of Wenzhou alumina producer) with the aqueous solution of sodium bromide dipping 0.5 hour, is under 110 ℃ of conditions dry 3 hours in temperature, obtains catalyst, and its character sees Table 1;
Sodium bromide is counted 0.5% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 2.0wt%, and then adding 1.5g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 365 ℃, constant temperature 1 minute takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 0.5% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 2.0wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 115-120 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 10 minutes, the outlet temperature of product is 360-370 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 0.5% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 5
Catalytic component: magnesium-modified η-Al
2O
335g beta-molecular sieve 15g
Contain potassium bromate 0.68g aqueous solution 30ml;
Preparation method: with magnesium-modified η-Al
2O
3(production of Wenzhou alumina producer) and beta-molecular sieve be with the aqueous solution of potassium bromate dipping 3 hours, is under 130 ℃ of conditions dry 1.5 hours in temperature, obtains catalyst, and its character sees Table 1;
Potassium bromate is counted 0.8% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 1.4wt%, and then adding 12g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 320 ℃, constant temperature 8 minutes takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 4% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 1.4wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 120-125 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 20 minutes, the outlet temperature of product is 350-360 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 4% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 6
Catalytic component: the θ-Al of phosphorus modification
2O
325g modenite 25g contains sodium bromate 1.61g aqueous solution 30ml;
Preparation method: with the θ-Al of phosphorus modification
2O
3(production of Wenzhou alumina producer) and modenite be with the aqueous solution of sodium bromate dipping 4 hours, is under 110 ℃ of conditions dry 12 hours in temperature, obtains catalyst, and its character sees Table 1;
Sodium bromate is counted 2% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 0.5wt%, and then adding 9.0g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 400 ℃, after reducing to room temperature product is taken out from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 3% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 0.5wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 125-130 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 30 minutes, the outlet temperature of product is 330-340 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 3% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 7
Catalytic component: the δ-Al of thorium modification
2O
310g MCM-41 type molecular sieve 40g
Contain boron bromide 1.59g aqueous solution 30ml;
Preparation method: with the δ-Al of thorium modification
2O
3(sale of capital, Jiyuan City engineering ceramic material Co., Ltd) and MCM-41 type molecular sieve be with the aqueous solution of boron bromide dipping 2.5 hours, is under 125 ℃ of conditions dry 10 hours in temperature, obtains catalyst, and its character sees Table 1;
Boron bromide is counted 3% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 1.6wt%, and then adding 3.0g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 330 ℃, constant temperature 20 minutes takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 1% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 1.6wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 120-130 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 40 minutes, the outlet temperature of product is 345-355 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 1% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 8
Catalytic component: the χ-Al of modified zirconia
2O
320g SAPO-5 type molecular sieve 30g contains sodium bromate 3.32g aqueous solution 30ml;
Preparation method: with the χ-Al of modified zirconia
2O
3(sale of capital, Jiyuan City engineering ceramic material Co., Ltd) and SAPO-5 type molecular sieve be with the aqueous solution of sodium bromate dipping 3.5 hours, is under 115 ℃ of conditions dry 8 hours in temperature, obtains catalyst, and its character sees Table 1;
Sodium bromate is counted 4% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 0.7wt%, and then adding 10g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 380 ℃, constant temperature 18 minutes takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 3.3% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 0.7wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 110-125 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 50 minutes, the outlet temperature of product is 340-345 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 3.3% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 9
Catalytic component: the γ-Al of niobium modification
2O
330g ZRP type molecular sieve 20g contains boron bromide 2.71g aqueous solution 30ml;
Preparation method: with the γ-Al of niobium modification
2O
3(sale of capital, Jiyuan City engineering ceramic material Co., Ltd) and ZRP type molecular sieve be with the aqueous solution of KBr dipping 1.5 hours, is under 113 ℃ of conditions dry 6 hours in temperature, obtains catalyst, and its character sees Table 1;
Boron bromide is counted 5% of catalyst weight with bromine in the catalyst.
Utilize above-mentioned catalyst to carry out the method that batch (-type) coal tar prepares fuel oil:
Adding the 300g moisture content in 1000ml reaction under high pressure kettle device is the coal tar of 1.2wt%, and then adding 6g catalyst, after reactor is airtight, the heating reactor makes it temperature and is elevated to 340 ℃, constant temperature 13 minutes takes out product after reducing to room temperature from reactor, carry out separated again, get 80-280 ℃ cut, promptly get fuel oil; Described catalyst is 2% of a coal tar weight, investigates the fuel oil properties, sees Table 2.
Utilize above-mentioned catalyst to carry out the method that continuous coal tar prepares fuel oil:
Moisture content is after the coal tar of 1.2wt% adds above-mentioned catalyst, is sent to one section in tube furnace by feedstock pump, is heated to 120-130 ℃ and enters one section evaporimeter dehydration.Coal tar after the dehydration and mixture of catalysts stop for two sections at tube furnace carried out catalytic reaction in 18 minutes, the outlet temperature of product is 350-360 ℃, product is carried out separated again after tube furnace is derived, get 80-280 ℃ cut, promptly gets fuel oil; Described catalyst is 2% of a coal tar weight, investigates the fuel oil properties, sees Table 3.
Embodiment 10
Catalytic component: rare earth modified γ-Al
2O
350g contains potassium bromate 5.63g aqueous solution 30ml;
Preparation of catalysts method and utilize this catalyst to carry out coal tar to prepare the method for fuel oil with embodiment 1; Wherein rare earth modified γ-Al
2O
3Sell by capital, Jiyuan City engineering ceramic material Co., Ltd;
Potassium bromate is counted 6% of catalyst weight with bromine in the catalyst of present embodiment.
Embodiment 11
Catalytic component: the γ-Al of magnesium and titanium modification
2O
350g contains sodium bromate 6.13g aqueous solution 30ml;
Preparation of catalysts method and utilize this catalyst to carry out coal tar to prepare the method for fuel oil with embodiment 2; γ-the Al of magnesium and titanium modification wherein
2O
3Sell by capital, Jiyuan City engineering ceramic material Co., Ltd;
Sodium bromate is counted 7% of catalyst weight with bromine in the catalyst of present embodiment.
Embodiment 12
Catalytic component: the γ-Al of modified zirconia
2O
3χ-the Al of 20g titanium modification
2O
330g contains sodium bromide 5.84g aqueous solution 30ml;
Preparation of catalysts method and utilize this catalyst to carry out coal tar to prepare the method for fuel oil with embodiment 4; γ-the Al of modified zirconia wherein
2O
3Sell by capital, Jiyuan City engineering ceramic material Co., Ltd;
Sodium bromide is counted 8% of catalyst weight with bromine in the catalyst of present embodiment.
Embodiment 13
Catalytic component: the γ-Al of thorium modification
2O
3θ-the Al of 15g niobium modification
2O
315g Y zeolite 20g contains potassium bromate 8.44g aqueous solution 30ml;
Preparation of catalysts method and utilize this catalyst to carry out coal tar to prepare the method for fuel oil with embodiment 3; γ-the Al of thorium modification wherein
2O
3γ-Al with the niobium modification
2O
3Sell by capital, Jiyuan City engineering ceramic material Co., Ltd;
Potassium bromate is counted 9% of catalyst weight with bromine in the catalyst of present embodiment.
Embodiment 14
Catalytic component: rare earth modified η-Al
2O
3δ-the Al of 25g titanium modification
2O
315g type ZSM 5 molecular sieve 10g contains KBr 7.52g aqueous solution 30ml;
Preparation of catalysts method and utilize this catalyst to carry out coal tar to prepare the method for fuel oil with embodiment 5; Wherein rare earth modified γ-Al
2O
3δ-Al with the titanium modification
2O
3Sell by capital, Jiyuan City engineering ceramic material Co., Ltd;
KBr is counted 10% of catalyst weight with bromine in the catalyst of present embodiment.
The prepared catalyst of embodiment 1-14 is spheric granules.
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| CN 201010563660 Pending CN102029174A (en) | 2010-11-25 | 2010-11-25 | Catalyst for producing fuel oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479354A (en) * | 2019-09-03 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of catalyst and preparation method thereof of the efficient process containing miscellaneous tar |
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| JPS5559846A (en) * | 1979-07-18 | 1980-05-06 | Hitachi Zosen Corp | Catalyst having activity at low temperature for exhaust smoke denitration |
| CN1120976A (en) * | 1995-08-16 | 1996-04-24 | 南开大学 | Catalyst for preparing styrene and ethylbenzene |
| US6403815B1 (en) * | 2001-11-29 | 2002-06-11 | Arco Chemical Technology, L.P. | Direct epoxidation process using a mixed catalyst system |
| CN1670127A (en) * | 2004-03-19 | 2005-09-21 | 张宪 | Hydrogenation conversion method for coal tar and catalyst therefor |
| CN101294107A (en) * | 2007-04-24 | 2008-10-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil with coal oil hydrogenation |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5559846A (en) * | 1979-07-18 | 1980-05-06 | Hitachi Zosen Corp | Catalyst having activity at low temperature for exhaust smoke denitration |
| CN1120976A (en) * | 1995-08-16 | 1996-04-24 | 南开大学 | Catalyst for preparing styrene and ethylbenzene |
| US6403815B1 (en) * | 2001-11-29 | 2002-06-11 | Arco Chemical Technology, L.P. | Direct epoxidation process using a mixed catalyst system |
| CN1670127A (en) * | 2004-03-19 | 2005-09-21 | 张宪 | Hydrogenation conversion method for coal tar and catalyst therefor |
| CN101294107A (en) * | 2007-04-24 | 2008-10-29 | 中国石油化工股份有限公司 | Method for preparing fuel oil with coal oil hydrogenation |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479354A (en) * | 2019-09-03 | 2019-11-22 | 黄河三角洲京博化工研究院有限公司 | A kind of catalyst and preparation method thereof of the efficient process containing miscellaneous tar |
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Application publication date: 20110427 |