CN108970614A - Fe-series catalyst, preparation method and application - Google Patents
Fe-series catalyst, preparation method and application Download PDFInfo
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- CN108970614A CN108970614A CN201810864204.8A CN201810864204A CN108970614A CN 108970614 A CN108970614 A CN 108970614A CN 201810864204 A CN201810864204 A CN 201810864204A CN 108970614 A CN108970614 A CN 108970614A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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Abstract
The present invention provides a kind of Fe-series catalyst, preparation method and applications.The preparation method includes: that 1) iron content soluble salt solutions are mixed and reacted with alkaline aqueous solution, obtains slurry head product；2) in the case where there is oxygen atmosphere, which is carried on solid carrier in spraying mode, carries out crystal transition, obtains the secondary product that the solid carrier surface has loaded FeOOH；And 3) in a nitrogen atmosphere, dry to the secondary product, obtain Fe-series catalyst.The preparation method process flow of Fe-series catalyst provided by the present invention is short, production cost is low, water consume is low, without waste water, by the DCL/Direct coal liquefaction catalytic activity height of catalyst prepared by the preparation method.
Description
Technical field
The present invention relates to coal chemical technologies, in particular to a kind of Fe-series catalyst, preparation method and application.
Background technique
Coal resources in China relative abundance, oil and natural gas resource relative shortage.DCL/Direct coal liquefaction is in high temperature and pressure
Under conditions of, by means of the effect of hydrogen supply dissolvent and catalyst, convert coal into the clean coal technology of product liquid.The technique
Major product is premium, jet fuel, diesel oil, aromatic hydrocarbons and carbon industrial chemicals, and by-product fuel gas, liquefied petroleum
Gas, sulphur and ammonia etc., process heat efficiency are up to 70%.Therefore DCL/Direct coal liquefaction production liquid fuel be coal cleaning conversion and efficiently
A kind of important channel utilized is the effective technology means for balancing the few oily regions resources of rich coal.The coal of the first megaton in China
Direct liquefaction production line from operation successful operation so far in 2008 9 years, carrying out second and Article 3 production line set
Meter and construction.
DCL/Direct coal liquefaction process is complicated physics, chemical process, and influence factor is numerous, specifically includes that the type of coal
And property, reactor types, catalyst, solvent, reaction temperature and time, atmosphere etc..Wherein, DCL/Direct coal liquefaction catalyst can
Promote the pyrolysis of coal and accelerates being hydrocracked for pyrolysis macromolecular, the quality of oily yield and oil in raising product, thus how
Exploitation and the hot spot that design catalytic activity is high, selective good and cheap catalyst is always DCL/Direct coal liquefaction research.
Most of Fe-series catalysts are cheap, and activity is preferable, suitable for once passing through the DCL/Direct coal liquefaction without recycling
Technique, thus it is more extensive to the research and application of Fe-series catalyst.The generated in-situ magnetic Huang iron in catalysis Coal liquefaction
Mine phase (Fe1-xS) has been the active phase of Fe-series catalyst by most researchers confirmation.Red mud, natural iron ore, synthesis type
Before iron sulfide, synthesis type ferriferous oxide and oil-soluble and water-soluble iron compound have all been used as catalyst for coal liquefaction
Body, but the nature differences such as their crystal phase structure, granularity and dispersibility are driven, will cause corresponding active phase property and catalysis coal liquid
Change effect and generates very big difference.There are many synthesis type Fe-series catalyst type and preparation method.To realize high activity, researcher is more
Pursue the iron presoma species for synthesizing lower granularity and more high degree of dispersion.
The preparation method of Fe-series catalyst in the prior art mainly has the defect of following several respects:
Defect one: it is larger to expend water, and the high difficult waste water of more salinity can be generated.
Defect two: preparation process flow is long and complicated, energy consumption is high, at high cost, is not suitable for large-scale development application.
Based on the above reasons, it needs further to study the preparation method of Fe-series catalyst, to solve the prior art
In the preparation method of Fe-series catalyst expend that water is big, process flow is long and complicated, energy consumption is high, at high cost, be not suitable for big rule
The problem of mould development and application.
Summary of the invention
The main purpose of the present invention is to provide a kind of Fe-series catalyst, preparation method and applications, to solve existing skill
The preparation method consuming water of Fe-series catalyst in art is big, process flow is long and complicated, energy consumption is high, at high cost, is not suitable for big
The problem of scale development is applied.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of preparation method of Fe-series catalyst,
The preparation method includes: that 1) iron content soluble salt solutions are mixed and reacted with alkaline aqueous solution, obtains slurry head product；2) exist
Have under oxygen atmosphere, which is carried on solid carrier in spraying mode, carries out crystal transition, obtain the solid carrier
The area load secondary product of FeOOH；And 3) in a nitrogen atmosphere, dry to the secondary product, obtain Fe-series catalyst.
Further, in step 1), under stiring, alkaline aqueous solution is added in iron content soluble salt solutions, is reacted
Afterwards, slurry head product is obtained.Preferably, which is the primary precipitation object Fe (OH) of iron2Or Fe (OH)3.Preferably,
The endpoint pH of the slurry head product controls between 7.5 to 9.0.
Further, in step 1), under stiring, by iron content soluble salt solutions and alkaline aqueous solution in a manner of cocurrent
Mixing, after reaction, obtains slurry head product.Preferably, which is the primary precipitation object Fe (OH) of iron2Or Fe
(OH)3.Preferably, the endpoint pH of the slurry head product controls between 7.0 to 9.0.
Further, in step 2), which is ball-type solid carrier.Preferably, which is coal dust.
Further, in step 2), be continually fed into a certain amount of air and form air atmosphere, at the same by the head product with
Spraying mode is sprayed on the coal dust surface quickly stirred, and the slurry head product of the iron precipitate then occurs on coal dust surface
It migrates and crystal transition occurs and generate FeOOH, to obtain the secondary product of coal dust area load FeOOH.
Further, the fogdrop diameter which forms by spraying is less than 300 μm.
Further, the temperature of the coal dust remains 60~120 DEG C.
Further, the partial size of the coal dust is less than 150 μm.
Further, in step 3), by the secondary product in 150~250 DEG C of dry 1~5h, Fe-series catalyst is obtained；
Preferably, the water content in the Fe-series catalyst is 1~4wt%；
Further, the Fe-series catalyst after drying is ground to 80 μm or less.
Further, the iron content in the prepared Fe-series catalyst is 1~6wt%.
Further, the iron content soluble-salt is in the group that ferrous sulfate, frerrous chloride, ferric sulfate and ferric nitrate form
It is one or more；Preferably, which is ferrous sulfate；Preferably, the concentration of the iron content soluble salt solutions
For 15~30wt%.
Further, which is the mixture of alkali and water, and the alkali is selected from ammonia, sodium carbonate and sodium hydroxide group
At one of group or a variety of.
Further, the concentration of the alkaline aqueous solution is 15~30wt%.
According to another aspect of the present invention, a kind of Fe-series catalyst is provided, is prepared according to the preparation method being described above
It forms.
According to another aspect of the present invention, a kind of Fe-series catalyst that basis is described above is provided in DCL/Direct coal liquefaction
Application in journey.
Apply the technical scheme of the present invention, the preparation method of Fe-series catalyst include: 1) by iron content soluble salt solutions with
Alkaline aqueous solution is mixed and is reacted, and obtains slurry head product；2) in the case where there is oxygen atmosphere, which is loaded in spraying mode
In on solid carrier, crystal transition is carried out, the secondary product that the solid carrier surface has loaded FeOOH is obtained；And 3) in nitrogen
It is dry to the secondary product under atmosphere, obtain Fe-series catalyst.
Wherein, it will first be precipitated in advance containing iron ion or ferrous ion and obtain the primary precipitation object of iron, then by spraying
Iron primary precipitation object is atomized into small liquid pearl by mode, is dripped on the solid carrier stirred, small liquid pearl is in solid carrier table
Occur migration infiltration inside face and duct, iron precipitate generates crystal transition while contraction, final to realize iron activity presoma
It uniformly closely loads on a solid carrier.
Compared to the liquid-phase precipitation method of traditional low concentration substrate, method for preparing catalyst provided by the present application is big with three
Outstanding advantages.One, preparation process flow is simpler.Traditional preparation methods include 5 steps such as precipitating-oxidation-filtering-drying-ball milling,
Each step is completed in different equipment, and present invention process merges oxidation-drying to be realized in a reactor, and is saved
Filtration step has been removed, therefore the cost of catalyst production cost and equipment investment will be greatlyd save at preparation end.Two, it can obviously mention
The DCL/Direct coal liquefaction catalytic activity of high catalyst.The Load Balanced degree and crystal phase of presoma are that two of Fe-series catalyst are most important
Property, it is closely related with DCL/Direct coal liquefaction catalytic activity；In method for preparing catalyst of the invention, in advance by precipitation of iron ions,
The solid carrier surface of heat is sprayed on by way of atomization again, step load and crystal transition is realized, crystalline substance can be strengthened first
Inversion of phases efficiency obtains more higher γ-FeOOH crystal phases of activity；Secondly, can be avoided iron precipitate filtering and it is dried
Journey it is hardened, so that the Load Balanced degree of active presoma on a solid carrier is increased dramatically, to improve DCL/Direct coal liquefaction
Catalytic activity.Three, substantially water-saving consumption-reduction and reduction discharge.Method for preparing catalyst of the invention is used when solution is prepared
The raw material of higher concentration, can be realized it is substantially water-saving, and liquid product without filtering, also do not generate waste water, moreover it is possible to avoid pressing
The problems such as filter plants such as filter are interrupted because of continuous production caused by excessively high failure rate.
Therefore, the preparation method process flow of Fe-series catalyst provided by the present invention is short, production cost is low, water consume is low,
Without waste water, by the DCL/Direct coal liquefaction catalytic activity height of catalyst prepared by the preparation method.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
As described in background technology part, the preparation method of existing Fe-series catalyst can not effectively solve consumption of water
The problem of amount is big, process flow is long and complexity, energy consumption are high, at high cost, is not suitable for large-scale development application.In order to solve above-mentioned ask
Topic, the present invention provides a kind of preparation method of Fe-series catalyst, the preparation method include: 1) by iron content soluble salt solutions with
Alkaline aqueous solution is mixed and is reacted, and obtains slurry head product；2) in the case where there is oxygen atmosphere, which is loaded in spraying mode
In on solid carrier, crystal transition is carried out, the secondary product that the solid carrier surface has loaded FeOOH is obtained；And 3) in nitrogen
It is dry to the secondary product under atmosphere, obtain Fe-series catalyst.
The preparation method process flow of Fe-series catalyst provided by the present invention is short, production cost is low, water consume is low, without useless
Water, by the DCL/Direct coal liquefaction catalytic activity height of catalyst prepared by the preparation method.
In a preferred embodiment, in step 1), under stiring, alkaline aqueous solution is added into iron content solubility
In salting liquid, after reaction, slurry head product is obtained.Preferably, which is the primary precipitation object Fe (OH) of iron2Or Fe
(OH)3.Preferably, the endpoint pH of the slurry head product controls between 7.5 to 9.0.Iron in the step 1) of the invention
The pH value of salt precipitating is 7.5~9.0, advantageously reduces the difficulty that FeOOH crystal phase species are generated in step 2), and lytic activity obtains
To further increase.
In a preferred embodiment, in step 1), under stiring, by iron content soluble salt solutions and alkaline water
Solution is mixed in a manner of cocurrent, after reaction, obtains slurry head product.Preferably, which is the primary precipitation object of iron
Fe(OH)2Or Fe (OH)3.Preferably, the endpoint pH of the slurry head product controls between 7.0 to 9.0.It will be in the step 1)
The pH value control of molysite deposition be 7.0~9.0, advantageously reduce the difficulty that FeOOH crystal phase species are generated in step 2), and produce
Object activity is further improved.
In a preferred embodiment, in step 2), which is ball-type solid carrier.Preferably, should
Solid carrier is coal dust.Compared to other solid carriers, coal dust used in the present invention, particle is thin, the coal dust of unit mass
With biggish surface area, the adsorbable large quantity of air in surface, to make it have mobility.
In a preferred embodiment, it in step 2), is continually fed into a certain amount of air and forms air atmosphere, together
When the head product is sprayed on the coal dust surface quickly stirred in spraying mode, the slurry head product of the iron precipitate is then
Occur to migrate and occur crystal transition generation FeOOH on coal dust surface, to obtain the secondary production of coal dust area load FeOOH
Object.In this step, iron primary precipitation object is atomized by small liquid pearl by spraying mode, dripped in the hot coal powder stirred
On, migration infiltration occurs inside coal dust surface and duct for small liquid pearl, and iron precipitate generates crystal transition while contraction, most
Realize that iron activity presoma uniformly closely loads on coal dust eventually.The step is sprayed on the coal dust of heat by way of atomization
Surface realizes step load and crystal transition, can strengthen crystal phase transformation efficiency first, obtains more higher γ-of activity
FeOOH crystal phase；Secondly, can be avoided iron precipitate filtering and drying process it is hardened, make active presoma on coal dust
Load Balanced degree is increased dramatically, to improve DCL/Direct coal liquefaction catalytic activity.
In a preferred embodiment, the fogdrop diameter which forms by spraying is less than 300 μm.It will in the present invention
The size Control of atomized drop is in the Fe (OH) for less than 300 μm, being beneficial to prevent excessive atomized drop and causing to be initially generated2
And/or Fe (OH)3Nanocrystal is easy the problem of being gathered into bulky grain, so that nanocrystal can be preferably in solid
Carrier surface spreads out, to form nanoscale FeOOH, further increases catalyst activity.
In a preferred embodiment, the temperature of the coal dust remains 60~120 DEG C.Temperature relative to other coal dusts
Degree, hot coal powder temperature is 60~120 DEG C in the present invention, is conducive to the primary precipitation of iron and realizes migration and on coal dust surface in time
Even load keeps Load Balanced degree further up, so that the primary precipitation object of iron is easily generated the FeOOH species of high activity, causes
Catalytic activity is substantially increased.
In a preferred embodiment, the partial size of the coal dust is less than 150 μm.Relative to other coal powder sizes, this hair
Bright coal powder size makes FeOOH be easy to be evenly distributed on coal dust surface, causes catalytic activity further up less than 150 μm.
In a preferred embodiment, in step 3), by the secondary product in 150~250 DEG C of dry 1~5h,
Obtain Fe-series catalyst；Preferably, the water content in the Fe-series catalyst is 1~4wt%.Relative to the dry temperature of other secondary products
It spends, controlling secondary product drying temperature in the present invention is 150~250 DEG C, is conducive to improve drying efficiency, and do not easily lead to work
Property presoma is decomposed.The water content in catalyst is controlled by adjusting drying time is 1~5h in the present invention, makes to be catalyzed
Water content control in agent is conducive to keep water partial pressure appropriate in coal liquefaction in 1~4wt%, further increases coal liquefaction effect
Rate further increases the stability of iron activity presoma, and the activity for being catalyzed DCL/Direct coal liquefaction is further up.
In a preferred embodiment, the Fe-series catalyst after drying is ground to 80 μm or less.In the present invention
Fe-series catalyst in catalyst is ground to 80 μm hereinafter, DCL/Direct coal liquefaction catalytic activity can be further increased.
In a preferred embodiment, the iron content in the prepared Fe-series catalyst is 1~6wt%.Relatively
Iron content control in other iron contents, the present invention in catalyst is 1~6wt%, and be conducive to saving preparation raw material uses water
Amount, further controls energy consumption；And the Load Balanced degree of the iron activity presoma on coal dust surface is further increased, activity is caused
It is further up.
In a preferred embodiment, which is selected from ferrous sulfate, frerrous chloride, ferric sulfate and nitre
One of group of sour iron composition is a variety of；Preferably, which is ferrous sulfate.Relative to other sources of iron, originally
Preferred source of iron is ferrous sulfate in invention, one is ferrous sulfate is at low cost, the second is ferrous sulfate generates under alkaline environment
Fe(OH)2Nanocrystal, more high activity γ-FeOOH crystal phases can be generated in oxidation by air in the drying process later.
In a preferred embodiment, the concentration of the iron content soluble salt solutions is 15~30wt%.Relative to it
His iron salt solutions concentration, iron salt solutions concentration requires to be 15~30wt% in the present invention, is conducive to the dosage for saving iron salt solutions,
Keep the slurry concentration to be formed moderate, keep coal dust water content moderate after being sprayed on coal dust surface, is easy to coal dust flowing, saves dry
Energy consumption, and keep catalyst precursor grain size moderate, cause catalyst activity to further increase.
In a preferred embodiment, which is the mixture of alkali and water, and the alkali is selected from ammonia, carbonic acid
One of group of sodium and sodium hydroxide composition is a variety of；Preferably, the concentration of the alkaline aqueous solution is 15~30wt%.Relatively
In other alkaline solution concentration, neutral and alkali solution concentration of the present invention requires to be 15~30wt%, is conducive to save alkaline solution
Dosage keeps the slurry concentration to be formed moderate, causes coal dust water content moderate after being sprayed on coal dust surface, is easy to coal dust flowing, section
Dry energy consumption is saved, and easily generates the FeOOH crystal phase species of high activity, causes catalyst activity further up.
In addition, according to another aspect of the present invention, a kind of Fe-series catalyst is provided, according to the preparation method being described above
It is prepared.
In addition, according to another aspect of the present invention, it is direct in coal to provide a kind of Fe-series catalyst that basis is described above
Application in liquefaction process.
Beneficial effects of the present invention are further illustrated by the following examples:
Embodiment 1
Being slowly dropped into ammonia spirit to the 900g concentration that concentration is 25wt% is in the ferrous sulfate solution of 25wt%, quickly
Stirring stops instilling when pH value reaches 7.5, and the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity and be less than
It is to open reaction kettle stirring and heat-conducting oil heating in 8L stirred autoclave that 150 μm of drying coal dust, which is placed in volume,.Work as coal dust
Temperature rises to 80 DEG C, is passed through the air of 2L/min, while the above-mentioned slurries prepared are delivered to reaction by plunger piston diaphragm pump
The spray head on kettle top is atomized, and atomizing pressure is adjusted, and controls fogdrop diameter within 300 μm, droplet is sprayed to the coal of stirring
Powder surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 180 DEG C, keeps 2h, makes to be catalyzed
Agent is dry, and catalyst is finally ground to 80 μm or less.Labeled as embodiment 1# catalyst.
Embodiment 2
The ferrous sulfate solution that 900g concentration is 25wt% is prepared, the ammonia spirit that 200g concentration is 25wt% is prepared, it will
Two kinds of solution are pumped into the beaker of 2L by peristaltic pump cocurrent to react, and quickly stirs, and the pH value for controlling reaction is 7.5 ± 0.1,
After the completion of ferrous sulfate solution all charging, stop charging reaction, the slurries of formation mix slowly for use.Subsequent step and reality
It is identical to apply example 1.Labeled as embodiment 2# catalyst.
Embodiment 3
Being slowly dropped into ammonia spirit to the 550g concentration that concentration is 25wt% is in the ferrous sulfate solution of 20wt%, quickly
Stirring stops instilling when pH value reaches 8.0, and the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity and be less than
It is to open reaction kettle stirring and heat-conducting oil heating in 8L stirred autoclave that 200 μm of drying coal dust, which is placed in volume,.Work as coal dust
Temperature rises to 60 DEG C, is passed through the air of 2L/min, while the above-mentioned slurries prepared are delivered to reaction by plunger piston diaphragm pump
The spray head on kettle top is atomized, and atomizing pressure is adjusted, and controls fogdrop diameter within 300 μm, droplet is sprayed to the coal of stirring
Powder surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 160 DEG C, keeps 3h, makes to be catalyzed
Agent is dry, and catalyst is finally ground to 80 μm or less.Labeled as embodiment 3# catalyst.
Embodiment 4
Being slowly dropped into sodium carbonate liquor to the 700g concentration that concentration is 15wt% is in the iron nitrate solution of 15wt%, quickly
Stirring stops instilling when pH value reaches 9.0, and the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity and be less than
It is to open reaction kettle stirring and heat-conducting oil heating in 8L stirred autoclave that 100 μm of drying coal dust, which is placed in volume,.Work as coal dust
Temperature rises to 60 DEG C, is passed through the air of 2L/min, while the above-mentioned slurries prepared are delivered to reaction by plunger piston diaphragm pump
The spray head on kettle top is atomized, and atomizing pressure is adjusted, and controls fogdrop diameter within 200 μm, droplet is sprayed to the coal of stirring
Powder surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 160 DEG C, keeps 4h, makes to be catalyzed
Agent is dry, and catalyst is finally ground to 80 μm or less.Labeled as embodiment 4# catalyst.
Embodiment 5
Being slowly dropped into sodium hydroxide solution to the 900g concentration that concentration is 30wt% is in the solution of ferrous chloride of 30wt%,
Quickly stirring stops instilling when pH value reaches 8.5, and the slurries of formation mix slowly for use.Weighing 2000g, to be ground to granularity small
Being placed in volume in 100 μm of drying coal dusts is to open reaction kettle stirring and heat-conducting oil heating in 8L stirred autoclave.Work as coal
Powder temperature rises to 120 DEG C, is passed through the air of 2L/min, while being delivered to the above-mentioned slurries prepared instead by plunger piston diaphragm pump
It answers the spray head on kettle top to be atomized, adjusts atomizing pressure, control fogdrop diameter within 250 μm, droplet is sprayed to stirring
Coal dust surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 200 DEG C, keeps 2h, makes to urge
Agent is dry, and catalyst is finally ground to 80 μm or less.Labeled as embodiment 5# catalyst.
Embodiment 6
It is quickly to stir in the ferrum sulfuricum oxydatum solutum of 18wt% that ammonia spirit that concentration is 25wt%, which is slowly dropped into, to 700g concentration
It mixes, stops instilling when pH value reaches 7.0, the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity less than 150
μm drying coal dust be placed in volume be 8L stirred autoclave in, open reaction kettle stirring and heat-conducting oil heating.When coal dust temperature
70 DEG C are risen to, is passed through the air of 2L/min, while the above-mentioned slurries prepared being delivered on reaction kettle by plunger piston diaphragm pump
The spray head in portion is atomized, and atomizing pressure is adjusted, and controls fogdrop diameter within 300 μm, droplet is sprayed to the coal dust table of stirring
Face.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 150 DEG C, keeps 3h, keeps catalyst dry
It is dry, catalyst is finally ground to 80 μm or less.Labeled as embodiment 6# catalyst.
Embodiment 7
Being slowly dropped into ammonia spirit to the 1700g concentration that concentration is 25wt% is in the ferrous sulfate solution of 20wt%, fastly
Speed stirring stops instilling when pH value reaches 7.5, and the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity and be less than
It is to open reaction kettle stirring and heat-conducting oil heating in 8L stirred autoclave that 150 μm of drying coal dust, which is placed in volume,.Work as coal dust
Temperature rises to 90 DEG C, is passed through the air of 2L/min, while the above-mentioned slurries prepared are delivered to reaction by plunger piston diaphragm pump
The spray head on kettle top is atomized, and atomizing pressure is adjusted, and controls fogdrop diameter within 300 μm, droplet is sprayed to the coal of stirring
Powder surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 220 DEG C, keeps 2h, makes to be catalyzed
Agent is dry, and catalyst is finally ground to 80 μm or less.Labeled as embodiment 7# catalyst.
Embodiment 8
Being slowly dropped into ammonia spirit to the 900g concentration that concentration is 25wt% is in the ferrous sulfate solution of 20wt%, quickly
Stirring stops instilling when pH value reaches 7.8, and the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity and be less than
It is to open reaction kettle stirring and heat-conducting oil heating in 8L stirred autoclave that 150 μm of drying coal dust, which is placed in volume,.Work as coal dust
Temperature rises to 110 DEG C, is passed through the air of 2L/min, while being delivered to the above-mentioned slurries prepared instead by plunger piston diaphragm pump
It answers the spray head on kettle top to be atomized, adjusts atomizing pressure, control fogdrop diameter within 230 μm, droplet is sprayed to stirring
Coal dust surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 250 DEG C, keeps 2.5h, makes
Catalyst is dry, and catalyst is finally ground to 80 μm or less.Labeled as embodiment 8# catalyst.
Embodiment 9
Being slowly dropped into ammonia spirit to the 1300g concentration that concentration is 20wt% is in the ferrous sulfate solution of 20wt%, fastly
Speed stirring stops instilling when pH value reaches 8.0, and the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity and be less than
It is to open reaction kettle stirring and heat-conducting oil heating in 8L stirred autoclave that 120 μm of drying coal dust, which is placed in volume,.Work as coal dust
Temperature rises to 60 DEG C, is passed through the air of 2L/min, while the above-mentioned slurries prepared are delivered to reaction by plunger piston diaphragm pump
The spray head on kettle top is atomized, and atomizing pressure is adjusted, and controls fogdrop diameter within 250 μm, droplet is sprayed to the coal of stirring
Powder surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 190 DEG C, keeps 3h, makes to be catalyzed
Agent is dry, and catalyst is finally ground to 80 μm or less.Labeled as embodiment 9# catalyst.
Embodiment 10
Being slowly dropped into ammonia spirit to the 1100g concentration that concentration is 20wt% is in the ferrum sulfuricum oxydatum solutum of 25wt%, quickly
Stirring stops instilling when pH value reaches 7.5, and the slurries of formation mix slowly for use.It weighs 2000g and is ground to granularity less than 80
μm drying coal dust be placed in volume be 8L stirred autoclave in, open reaction kettle stirring and heat-conducting oil heating.When coal dust temperature
100 DEG C are risen to, is passed through the air of 2L/min, while the above-mentioned slurries prepared are delivered to by reaction kettle by plunger piston diaphragm pump
The spray head on top is atomized, and atomizing pressure is adjusted, and controls fogdrop diameter within 300 μm, droplet is sprayed to the coal dust of stirring
Surface.It finishes by spraying, is switched to nitrogen, increasing reaction kettle heating temperature makes coal dust be warming up to 240 DEG C, keeps 2h, makes catalyst
It is dry, catalyst is finally ground to 80 μm or less.Labeled as embodiment 10# catalyst.
Comparing embodiment 11
With the difference of embodiment 1 are as follows: ferrous sulfate solution concentration is 10wt%.Labeled as comparing embodiment 11# catalyst.
Comparing embodiment 12
With the difference of embodiment 1 are as follows: ferrous sulfate solution concentration is 35wt%.Labeled as comparing embodiment 12# catalyst.
Comparing embodiment 13
With the difference of embodiment 1 are as follows: the concentration of ammonia spirit is 10wt%.Labeled as comparing embodiment 13# catalyst.
Comparing embodiment 14
With the difference of embodiment 1 are as follows: the concentration of ammonia spirit is 35wt%.Labeled as comparing embodiment 14# catalyst.
Comparing embodiment 15
With the difference of embodiment 1 are as follows: reaction end pH is 6.0.Labeled as comparing embodiment 15# catalyst.
Comparing embodiment 16
With the difference of embodiment 1 are as follows: reaction end pH is 9.5.Labeled as comparing embodiment 16# catalyst.
Comparing embodiment 17
With the difference of embodiment 2 are as follows: fogdrop diameter is within 400 μm.Labeled as comparing embodiment 17# catalyst.
Comparing embodiment 18
With the difference of embodiment 1 are as follows: granularity is less than 250 μm.Labeled as comparing embodiment 18# catalyst.
Comparing embodiment 19
With the difference of embodiment 1 are as follows: the control of coal dust temperature is 40 DEG C during spraying and crystal transition.Labeled as relatively more real
Apply a 19# catalyst.
Comparing embodiment 20
With the difference of embodiment 1 are as follows: the control of coal dust temperature is 150 DEG C during spraying and crystal transition.Labeled as comparing
Embodiment 20# catalyst.
Comparing embodiment 21
With the difference of embodiment 1 are as follows: the drying temperature under nitrogen atmosphere is 280 DEG C.It is catalyzed labeled as comparing embodiment 21#
Agent.
Comparing embodiment 22
With the difference of embodiment 1 are as follows: the drying time under nitrogen atmosphere is 0.5h.It is catalyzed labeled as comparing embodiment 22#
Agent.
Comparing embodiment 23
With the difference of embodiment 1 are as follows: the drying time under nitrogen atmosphere is 6h.Labeled as comparing embodiment 23# catalyst.
Comparative example 1
The FeOOH catalyst of coal dust load is prepared using liquid-phase precipitation oxidation:
Being slowly dropped into ammonia spirit to the 900g concentration that concentration is 25wt% is in the ferrous sulfate solution of 25wt%, quickly
Stirring stops instilling when pH value reaches 7.5；It is passed through the air oxidation 1h of 2L/min, generates slurries containing FeOOH after having reacted,
Be added 2000g granularity be 150 μm within dry pulverized coal, stir, the mixed serum filtering, obtain filter cake addition go from
Sub- water carries out mashing washing, and the filter cake after washing is put into 120 DEG C of nitrogen drying boxes dry 12h, after dry that solid is finely ground
To 80 μm hereinafter, obtaining the FeOOH powder catalyst of coal dust load.Labeled as contrast medium 1.
Catalyst performance evaluation
The catalyst in a certain amount of above-described embodiment 1 to 21 in catalyst obtained and comparative example 1 is weighed respectively carries out coal
The test of liquefying high pressure kettle, Coal liquefaction performance test conditions are as follows: obtained in accurate weighing above-described embodiment 1 to 21 respectively
Catalyst in catalyst and comparative example 1, and final catalyst is added in 500mL autoclave Coal liquefaction.Test institute
It is the eastern coal of Shenhua mind with coal sample, the additional amount of dry pulverized coal is 28g；Using coal liquefaction recycle oil as solvent, solvent adding amount 42g,
Each catalyst measurement criteria being added is that Fe/ dry coal weight ratio is 1:100, and 0.32g sulphur powder is added.At the beginning of autoclave reacts cold hydrogen
Pressure is 10MPa, constant temperature 1h, end of reaction at 455 DEG C.Reaction system is quickly cooled down, gas sample is taken to survey its composition, is collected anti-
Liquid-solid phase after answering will extract residue ashing, calculate and obtain coal respectively by n-hexane and tetrahydrofuran Soxhlet extraction 48h
The data such as conversion ratio, hydrogen consumption, gas yield, aquatic products rate, pitch yield, oil yield, are specifically shown in Table 1.
Table 1
The most key index of DCL/Direct coal liquefaction oil yield catalytic performance, to megaton DCL/Direct coal liquefaction commercial plant
Speech, the minor fluctuations of oil yield all can generate strong influence to DCL/Direct coal liquefaction economy.
It can from embodiment 1, comparing embodiment 11, comparing embodiment 12 it can be seen from coal liquefaction experimental result in table 1
Know, iron salt concentration is limited to the catalytic performance for being conducive to improve catalyst in the preferred protection scope of the application.In the present invention
Iron salt solutions concentration requires to be 15~30wt%, and the slurry concentration of formation is moderate, makes coal dust water content after being sprayed on coal dust surface
It is moderate, it is easy to coal dust flowing, catalyst precursor grain size is moderate, and catalyst activity rises.
It is found that the concentration of lye is limited to the application is excellent from embodiment 1, comparing embodiment 13, comparing embodiment 14
Be conducive to improve the catalytic performance of catalyst in the protection scope of choosing.Neutral and alkali solution concentration of the present invention requires as 15~
30wt% keeps the slurry concentration to be formed moderate, causes coal dust water content moderate after being sprayed on coal dust surface, is easy to coal dust flowing,
The FeOOH crystal phase species of high activity are generated, catalyst activity rises.
It is found that the pH value of reaction is limited to the application is excellent from embodiment 1, comparing embodiment 15, comparing embodiment 16
The catalytic performance for being conducive to improve catalyst in the protection scope of choosing makes the difficulty drop for generating the FeOOH crystal phase species of high activity
It is low, increase lytic activity.
It is found that the granularity of atomized drop, which is limited to the application, preferably protects model from embodiment 1, comparing embodiment 17
Be conducive to improve the catalytic performance of catalyst in enclosing.Atomized drop makes the Fe (OH) being initially generated less than 300 μm in the present invention2
And/or Fe (OH)3Nanocrystal is not easy to be gathered into bulky grain, easily disperses on coal dust surface, forms nanoscale FeOOH, makes to be catalyzed
Agent activity rises.
From in embodiment 1, comparing embodiment 18 it is found that coal powder size is limited in the preferred protection scope of the application has
Conducive to the catalytic performance for improving catalyst.Coal powder size of the present invention makes FeOOH be evenly distributed on coal dust surface, leads less than 150 μm
Activation rises.
It is from embodiment 1, comparing embodiment 19, comparing embodiment 20 it is found that the limit temperature of coal dust is excellent in the application
Be conducive to improve the catalytic performance of catalyst in the protection scope of choosing.Hot coal powder temperature is 60~120 DEG C in the present invention, leads to iron
Primary precipitation coal dust surface realize migration and uniform load, make Load Balanced degree rise, generate the FeOOH object of high activity
Kind, cause catalytic activity to be substantially increased；Be conducive to crystal transition and generate higher active γ-FeOOH species.
From in embodiment 1, comparing embodiment 21 it is found that drying temperature is limited in the preferred protection scope of the application has
Conducive to the catalytic performance for improving catalyst.Controlling secondary product drying temperature in the present invention is 150~250 DEG C, makes drying efficiency
Rise, while not will lead to active presoma and decomposing.
It is found that the drying time of secondary product is limited to this from embodiment 1, comparing embodiment 22, comparing embodiment 23
Apply for the catalytic performance for being conducive to improve catalyst in preferred protection scope.In the present invention by adjusting drying time be 1~
5h controls the water content in catalyst, controls the water content in catalyst in 1~4wt%, is moisture positive pressure in coal liquefaction
Often, increase coal liquefaction efficiency, increase the stability of iron activity presoma, the activity for being catalyzed DCL/Direct coal liquefaction rises.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
Using the corresponding liquefied coal coil yield of major part catalyst made from method provided by the present application better than contrast medium or
It is suitable with contrast medium, there is the corresponding oil yield of small part catalyst to be worse than contrast medium, it is contemplated that preparation provided by the present application
Method and process is simple, energy-saving obvious, and the preparation method of Fe-series catalyst provided by the present application has huge in coal chemical technology
Big economic benefit.Method for preparing catalyst device therefor of the invention simultaneously is less, and operating cost is less, and Water usage
Lack, not efflux wastewater.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of Fe-series catalyst, which is characterized in that the preparation method includes:
1) iron content soluble salt solutions are mixed and is reacted with alkaline aqueous solution, obtain slurry head product；
2) in the case where there is oxygen atmosphere, the head product is carried on solid carrier in spraying mode, carries out crystal transition, obtains
The solid carrier surface has loaded the secondary product of FeOOH；And
3) in a nitrogen atmosphere, dry to the secondary product, obtain the Fe-series catalyst.
2. the preparation method of Fe-series catalyst according to claim 1, which is characterized in that in the step 1), stirring
It mixes down, the alkaline aqueous solution is added in the iron content soluble salt solutions, after reaction, obtain the slurry head product.
3. the preparation method of Fe-series catalyst according to claim 1, which is characterized in that in the step 1), stirring
It mixes down, the iron content soluble salt solutions is mixed in a manner of cocurrent with the alkaline aqueous solution, after reaction, obtain the slurry
Head product.
4. the preparation method of Fe-series catalyst according to any one of claim 1 to 3, which is characterized in that in the step
It is rapid 2) in, the solid carrier be ball-type solid carrier；Preferably, the solid carrier is coal dust；Preferably, the head product
The fogdrop diameter formed by spraying is less than 300 μm；Preferably, the temperature of the coal dust remains 60~120 DEG C；Preferably, described
The partial size of coal dust is less than 150 μm.
5. the preparation method of Fe-series catalyst according to any one of claim 1 to 3, which is characterized in that in the step
It is rapid 3) in, by the secondary product in 150~250 DEG C of dry 1~5h, obtain the Fe-series catalyst；Preferably, the iron series are urged
Water content in agent is 1~4wt%；Preferably, the Fe-series catalyst after drying is ground to 80 μm or less；It is preferred that
Ground, the iron content in the prepared Fe-series catalyst are 1~6wt%.
6. the preparation method of Fe-series catalyst according to any one of claim 1 to 3, which is characterized in that the iron content
Soluble-salt is selected from one of group of ferrous sulfate, frerrous chloride, ferric sulfate and ferric nitrate composition or a variety of；Preferably, institute
Stating iron content soluble-salt is ferrous sulfate；The concentration of the iron content soluble salt solutions is 15~30wt%；Preferably, the alkali
Property aqueous solution be alkali and water mixture, the alkali is selected from one of group or a variety of of ammonia, sodium carbonate and sodium hydroxide composition；
Preferably, the concentration of the alkaline aqueous solution is 15~30wt%.
7. the preparation method of Fe-series catalyst according to claim 2, which is characterized in that by the end of the slurry head product
Point pH value control is between 7.5 to 9.0.
8. the preparation method of Fe-series catalyst according to claim 3, which is characterized in that by the end of the slurry head product
Point pH value control is between 7.0 to 9.0.
9. a kind of Fe-series catalyst, which is characterized in that be prepared by preparation method described in any item of the claim 1 to 8.
10. a kind of application of Fe-series catalyst as claimed in claim 9 during DCL/Direct coal liquefaction.
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| CN111573883A (en) * | 2020-04-21 | 2020-08-25 | 生态环境部华南环境科学研究所 | Method for treating chemical nickel plating waste liquid through iron-based catalyst |
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