CN107159271A - The common artificial coal loaded catalyst of kerosene hydrogenation, preparation method and applications - Google Patents
The common artificial coal loaded catalyst of kerosene hydrogenation, preparation method and applications Download PDFInfo
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- CN107159271A CN107159271A CN201710401352.1A CN201710401352A CN107159271A CN 107159271 A CN107159271 A CN 107159271A CN 201710401352 A CN201710401352 A CN 201710401352A CN 107159271 A CN107159271 A CN 107159271A
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- coal
- molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
The present invention proposes a kind of kerosene hydrogenation artificial coal loaded catalyst, preparation method and applications altogether, including active component, helps composition living and carrier, and the active component is iron and molybdenum, and the molal weight ratio of the iron and the molybdenum is 35:1~1:1, the iron is water-soluble molysite, and the molybdenum is water-soluble molybdenum salt, described to help composition living for sulfide, and the molal weight ratio of the sulfide and the active component is 1:3~1:5, the carrier is coal dust.Preparation method：1) molysite and molybdenum salt are weighed, is then added to the water and mixed salt solution is made；2) sulfide and appropriate alcohol are added into salt mixed liquor, is uniformly mixed, then after warming while stirring to preference temperature, adds coal dust and is reacted；3) step 2) reaction terminate after be cooled to room temperature, drying.The catalyst not only has the advantages that hydrogenation activity is high, the burnt effect of suppression is good and coal high conversion rate, also prepares simply, suitable for large-scale industrial production.
Description
Technical field
Catalyst technical field is refined altogether the invention belongs to oily coal hydrogenation, and in particular to a kind of coal-oil hydrogenation artificial coal load altogether
Type catalyst, preparation method and applications.
Background technology
On the one hand, heaviness, in poor quality with crude oil, and the increase year by year to light-end products demand, heavy oil are special
It is development trend of the working process as oil refining factory of high carbon residue, high-sulfur nitrogen, high metal poor residuum.On the other hand, China
Rich coal resources, proven reserve is only second to the U.S., Russia.The direct burning of a large amount of coals is brought more to environmental protection
Carry out more white elephant.To solve the problems, such as oily coal utilization, coal-oil floating bed hydrogenation refines technology and given birth to therefrom altogether.It can be utilized
Coal dust and synergy heavy, between residual oil, make coal liquefaction make heavy oil lighting, particularly slag while being converted into liquid fuel
The removing of metallic element in oil, improves the utilization level of heavy oil.
Coal-oil floating bed hydrogenation altogether sweetening process be under the atmosphere of hydrogen, coal dust and again, residual oil is in the presence of catalyst
Hydrocracking reaction is carried out by reactor.Catalyst is coal-oil floating bed hydrogenation one of key technology of sweetening process altogether.The work
Skill catalyst disposably passes through, and catalyst preparation is simple, and dosage is few, and catalytic activity is high, and metal recovery rate is high, reduces cost.
Fe-series catalyst because its price is low, it is small to pollute, receive significant attention the advantages of need not reclaim, but Fe-series catalyst activity compared with
It is low, and be difficult input practical application for higher Co, Mo, Mo and W series catalysts of activity, and because of its high cost, so uncommon
Hope that ferrum-based catalyst and Mo, Mo of relatively small amount high price etc. is compound, it is desirable to while ferrum-based catalyst activity is improved, subtract
The consumption of few high price metal.Therefore, a kind of coal load Fe-Mo bimetallic catalysts are researched and developed particularly important.
United States Patent (USP) US4298454 is urged using catalyst is obtained after the decomposition and vulcanization of the metallic compound of support type molybdenum
The addition of agent is 10~950 μ gg-1(in terms of metal), but according to its experimental result only in 1000 μ gg-1, and
And catalyst is needed in H2S/H2Can just there is preferable reaction effect after being pre-processed in atmosphere.Grant number is in CN102309972
State's patent discloses a kind of catalyst, and it is catalyzed by major catalyst, secondary catalyst and the part of auxiliary agent three composition, major catalyst for iron-based
Agent, addition is 0.2%~5.0%, and secondary catalyst is catalyst with base of molybdenum, and addition is that Fe and Mo mol ratios are 50：1-200：
1, auxiliary agent is Cosan or sulfur-bearing thing, and S/ (Fe+Mo) mol ratio is 1：4.Reaction is divided into two stages, first stage reaction temperature
For 300~410 DEG C, reaction pressure is 8~20MPa, and the reaction time is that 10~60min second stage reaction temperatures are 380~470
DEG C, reaction pressure is 8~22MPa, and the reaction time is 30~120min.After reaction<500 degrees Celsius of yields reach 60m%
More than, conversion ratio can reach more than 90m%.The preparation method of this method catalyst is complicated, and Mo metal prices are higher.
Refining process is divided into two steps altogether, and reaction temperature is higher, and process is complicated.
The content of the invention
The present invention proposes a kind of coal-oil hydrogenation artificial coal loaded catalyst altogether, the catalyst not only have hydrogenation activity height,
The advantages of pressing down good burnt effect and coal high conversion rate, also prepare simply, suitable for large-scale industrial production.
The technical proposal of the invention is realized in this way：
A kind of coal-oil hydrogenation artificial coal loaded catalyst altogether, including active component, help composition living and carrier, the work
Property composition be iron and molybdenum, the molal weight ratio of the iron and the molybdenum is 35:1~1:1, the iron is water-soluble molysite, described
Molybdenum is water-soluble molybdenum salt, described to help composition living for sulfide, and the molal weight ratio of the sulfide and the active component is 1:3
~1:5, the carrier is coal dust.
Preferably, one or more of the coal dust in lignite, ub-bituminous coal and bituminous coal.
Preferably, the molysite is the one or more in ferrous sulfate, iron chloride, ferric nitrate.
Preferably, the molybdenum salt is the one or more in ammonium molybdate, ammonium thiomolybdate, sodium molybdate.
Preferably, the sulfide is selected from vulcanized sodium, hydrogen sulfide, carbon disulfide and the one or more in vulcanization ammonia.
It is a further object to provide a kind of preparation method of coal-common artificial coal loaded catalyst of oil hydrogenation, bag
Include following steps：
1) molysite and molybdenum salt are weighed, is then added to the water and mixed salt solution is made；
2) sulfide and appropriate alcohol are added into salt mixed liquor, is uniformly mixed, then warming while stirring is to suitable
After temperature, add coal dust and reacted；
3) step 2) reaction terminate after be cooled to room temperature, drying.
Preferably, the step 2) in appropriate surfactant can also be added to salt mixed liquor.Add surface-active
The purpose of agent is further raising molysite and dispersiveness of the molybdenum salt in coal dust.
Preferably, the step 2) 50~100 DEG C are warming up to, the time of reaction is 1~4h.
Preferably, the surfactant is selected from sodium carboxymethylcellulose, lauryl sodium sulfate, polyvinylpyrrolidine
One or more in ketone, cetyl trimethylammonium bromide.
Preferably, the alcohol is the one or more in methanol, ethanol, propyl alcohol and polyethylene glycol.
It is also another object of the present invention to provide a kind of application of coal-oil hydrogenation artificial coal loaded catalyst altogether, add coal-
The total metal content of catalyst in oil is 200~2000 μ gg-1 of coal-oil.
Beneficial effects of the present invention：
1st, on the basis of grant number is CN102309972 Chinese patent, it is suitable in order to simplify preparation technology
Scale industrial production, inventor is attempted water-soluble molysite and water-soluble molybdenum salt carrying out load processing, and discovery is supported on
Industrialized in carrier such as activated carbon powder, carbon powder etc. before coal dust relatively difficult.Dispersant needed for load, sends out in surprise
Existing alcohol can be good at water-soluble molysite and water-soluble molybdenum salt being supported in coal dust, while will can also vulcanize as dispersant
Thing is loaded wherein, is conducive to its activity of sulfide co-catalysis.
2nd, the catalyst bimetallic mol ratio prepared by the present invention is flexibly adjustable, and the addition of a small amount of molybdenum compensate for the catalysis of iron system
, there is therebetween synergy in the inferior position that agent activity is not enough, hydrogenation activity is high, and the burnt effect of suppression is good, coal high conversion rate.
Embodiment
Embodiment 1
A kind of coal-oil hydrogenation artificial coal loaded catalyst altogether, including active component, help composition living and carrier, the work
Property composition be iron and molybdenum, the molal weight ratio of the iron and the molybdenum is 1:1, the iron is ferrous sulfate, and the molybdenum is molybdic acid
Sodium, described to help composition living to be vulcanized sodium, the carrier is coal dust.
Preparation method is as follows：
1) by 0.2576g sodium molybdates, 0.7948g ferrous sulfate is added in 100ml deionized waters；
2) 20ml propyl alcohol, 0.2g neopelexes and 0.6860g vulcanized sodium are added into mixed liquor；
3) 50 DEG C under stirring, are heated the solution to, 100g coal dusts, reaction time 1h is added；
4) a period of time is placed after reaction terminates in an oven, you can.
Embodiment 2
A kind of coal-oil hydrogenation artificial coal loaded catalyst altogether, including active component, help composition living and carrier, the work
Property composition be iron and molybdenum, the molal weight ratio of the iron and the molybdenum is 3:1, the iron is ferrous sulfate, and the molybdenum is molybdic acid
Sodium, described to help composition living to be vulcanized sodium, the carrier is coal dust.
Preparation method：
1) by 0.2576g sodium molybdates, 2.3940g ferrous sulfate is added in 100ml deionized waters；
2) 20ml polyethylene glycol, 0.2g neopelexes and 2.067g vulcanized sodium are added into mixed liquor；
3) 80 DEG C under stirring, are heated the solution to, 100g coal dusts, reaction time 1h is added；
4) a period of time is placed after reaction terminates in an oven, you can.
Embodiment 3
A kind of coal-oil hydrogenation artificial coal loaded catalyst altogether, including active component, help composition living and carrier, the work
Property composition be iron and molybdenum, the molal weight ratio of the iron and the molybdenum is 9:1, the iron is ferrous sulfate, and the molybdenum is molybdic acid
Sodium, described to help composition living to be vulcanized sodium, the carrier is coal dust.
Preparation method：
1) by 0.2576g sodium molybdates, 7.1820g ferrous sulfate is added in 100ml deionized waters；
2) 20ml ethanol, 0.2g neopelexes and 6.2010g vulcanized sodium are added into mixed liquor；
3) 100 DEG C under stirring, are heated the solution to, 100g coal dusts, reaction time 1h is added；
4) a period of time is placed after reaction terminates in an oven, you can.
Test example
Artificial coal loaded catalyst catalytic effect is similar altogether for embodiment 1-3 coal-oil hydrogenation, now with the coal of embodiment 1-
During the common artificial coal loaded catalyst of oil hydrogenation is refined altogether for the hydrogenation of the auspicious reduced crude of horse and Anhui coal, and using blank, load
The reaction that type ammonium molybdate catalyst, support type ferrous sulfate catalyst are carried out under the same terms is in contrast.The auspicious reduced crude of horse
Property is shown in Table 1, and Anhui coal property is shown in Table 2, and reaction condition is：400 DEG C of reaction temperature, reacts first pressing 8MPa, the auspicious reduced crude of horse：
Anhui coal=3:1, reaction time 60min, the μ gg-1 of vulcanizing agent 2000；Reaction result is shown in Table 3.
The auspicious reduced crude fundamental property of the horse of table 1
The Industrial Analysis of the Anhui coal of table 2 and element composition and property
The Ma Ruichang slags of table 3-Anhui coal hydrogenation refines distribution of reaction products altogether
As shown in Table 3, relative to using support type Mo catalyst, support type Fe catalyst, using the catalyst of embodiment 1
(Fe-Mo(1：1) coking yield of reaction system is minimum when)；From solid productivity, coal conversion ratio, the catalyst of embodiment 1 exceedes
The catalytic effect of support type molybdenum, from the point of view of coal-oil hydrogenation altogether refining product yield, support type Fe-Mo (1：1) bimetallic catalyst exists
While suppressing green coke, can also heavy oil be promoted to change to light component.The catalyst of the present invention not only improves reaction effect, also big
The big production cost for reducing catalyst (because cheap metal Fe introducing instead of the metal of a part of high price).
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (10)
1. a kind of coal-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that including active component, help composition living and load
Body, the active component is iron and molybdenum, and the molal weight ratio of the iron and the molybdenum is 35:1~1:1, the iron is water solubility
Molysite, the molybdenum is water-soluble molybdenum salt, described to help composition living to be sulfide, mole matter of the sulfide and the active component
Amount is than being 1:3~1:5, the carrier is coal dust.
2. the coal according to claim 1-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that the coal dust is selected from
One or more in lignite, ub-bituminous coal and bituminous coal.
3. the coal according to claim 1-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that the molysite is sulphur
One or more in sour ferrous iron, iron chloride, ferric nitrate.
4. the coal according to claim 1-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that the molybdenum salt is molybdenum
One or more in sour ammonium, ammonium thiomolybdate, sodium molybdate.
5. the coal according to claim 1-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that the sulfide choosing
Autovulcanization sodium, hydrogen sulfide, carbon disulfide and the one or more in vulcanization ammonia.
6. the preparation method of coal as claimed in claim 1-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that including
Following steps：
1) molysite and molybdenum salt are weighed, is then added to the water and mixed salt solution is made；
2) sulfide and appropriate alcohol are added into salt mixed liquor, is uniformly mixed, then warming while stirring is to preference temperature
Afterwards, coal dust is added to be reacted；
3) step 2) reaction terminate after be cooled to room temperature, drying.
7. the preparation method of coal according to claim 6-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that institute
State step 2) in appropriate surfactant can also be added to salt mixed liquor.
8. the preparation method of coal-common artificial coal loaded catalyst of oil hydrogenation according to claim 6 or 7, it is characterised in that
The step 2) 50~100 DEG C are warming up to, the time of reaction is 1~4h.
9. the preparation method of coal according to claim 7-common artificial coal loaded catalyst of oil hydrogenation, it is characterised in that institute
State surfactant and be selected from sodium carboxymethylcellulose, lauryl sodium sulfate, polyvinylpyrrolidone, cetyl trimethyl bromine
Change the one or more in ammonium.
10. the application of coal-common artificial coal loaded catalyst of oil hydrogenation as described in claim 1 to 5 any one, its feature exists
In the total metal content of the catalyst added in coal-oil is 200~2000 μ gg-1 of coal-oil.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108298508A (en) * | 2018-04-04 | 2018-07-20 | 西北大学 | Two sulphur oxygen molybdenums and its synthetic method and application |
| CN109647535A (en) * | 2018-12-28 | 2019-04-19 | 中国船舶重工集团公司第七八研究所 | A kind of loaded ferrum-based catalyst of coal |
| CN111841630A (en) * | 2020-06-24 | 2020-10-30 | 中国石油大学(华东) | Fatty acid nickel oil-soluble catalyst for coal/heavy oil hydrogenation co-refining and application thereof |
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| CN102309972A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Oil coal hydrogenation mixing catalyst and mixing method thereof |
| CN102732295A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
| CN106693975A (en) * | 2016-11-24 | 2017-05-24 | 中国石油大学(华东) | Oil-soluble Fe-Ni bimetallic catalyst, and preparation method and application of bimetallic catalyst |
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2017
- 2017-05-31 CN CN201710401352.1A patent/CN107159271A/en active Pending
Patent Citations (3)
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| CN102309972A (en) * | 2010-06-29 | 2012-01-11 | 中国石油化工股份有限公司 | Oil coal hydrogenation mixing catalyst and mixing method thereof |
| CN102732295A (en) * | 2011-04-14 | 2012-10-17 | 中国石油化工股份有限公司 | Preparation method of coal-oil slurry coprocessed by coal-oil hydrogenation, coal-oil slurry and its coprocessing method |
| CN106693975A (en) * | 2016-11-24 | 2017-05-24 | 中国石油大学(华东) | Oil-soluble Fe-Ni bimetallic catalyst, and preparation method and application of bimetallic catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108298508A (en) * | 2018-04-04 | 2018-07-20 | 西北大学 | Two sulphur oxygen molybdenums and its synthetic method and application |
| CN108298508B (en) * | 2018-04-04 | 2019-09-10 | 西北大学 | Two sulphur oxygen molybdenums and its synthetic method and application |
| CN109647535A (en) * | 2018-12-28 | 2019-04-19 | 中国船舶重工集团公司第七八研究所 | A kind of loaded ferrum-based catalyst of coal |
| CN111841630A (en) * | 2020-06-24 | 2020-10-30 | 中国石油大学(华东) | Fatty acid nickel oil-soluble catalyst for coal/heavy oil hydrogenation co-refining and application thereof |
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Application publication date: 20170915 |