CN105664946A - Solid phase preparation method for iron-based catalyst for direct coal liquefaction - Google Patents
Solid phase preparation method for iron-based catalyst for direct coal liquefaction Download PDFInfo
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- CN105664946A CN105664946A CN201610008686.8A CN201610008686A CN105664946A CN 105664946 A CN105664946 A CN 105664946A CN 201610008686 A CN201610008686 A CN 201610008686A CN 105664946 A CN105664946 A CN 105664946A
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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
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
The invention provides a solid phase preparation method for an iron-based catalyst for catalyzing a direct liquefaction reaction of coal. In the method, with pulverized coal as a carrier material, a solid phase chemical reaction of an iron-based metal salt and an alkali is carried out at room temperature, an iron-based metal oxide (hydroxide) loaded on the coal is prepared, and the iron-based metal oxide (hydroxide)/coal composite material is used as the catalyst for direct liquefaction reaction of the coal and shows relatively good catalytic effect. In the composite catalyst, the active component iron-based metal oxide (hydroxide) has relatively small size, has good contact with the coal carrier and is uniformly distributed on the carrier, so that the catalyst has relatively high catalytic activity and can effectively promote conversion and liquefaction of the coal. The method has the advantages of cheap and easily obtained used raw materials, simple reaction operation and less time consuming, is prone to mass production, and has wide application prospect.
Description
Technical field
The invention belongs to the Direct liquefaction technology field of coal, the preparation method relating in particular to a kind of ferrum system DCL/Direct coal liquefaction catalyst.
Background technology
How sufficiently and reasonably utilizing coal resources is our currently encountered major issue. Direct coal liquefaction technology, as the effective means of a kind of clean coal utilization, increasingly causes the attention of people. DCL/Direct coal liquefaction reaction refers to that coal is at suitable temperature and Hydrogen Vapor Pressure, under the existence condition of solvent and catalyst, is converted into the process of liquid hydrocarbon. In this course of reaction, catalyst plays an important role. Excellent catalyst is possible not only to reduce severity and the production cost of reaction condition, and can improve liquid product yield and oil quality. In current studied all kinds of catalyst, Fe-series catalyst causes extensive concern with the advantage of its uniqueness. Especially iron-containing catalyst, it is cheap, environmental sound, presents huge application advantage.
Research shows, reduces catalyst particle size, improves catalyst dispersion in liquefaction system, is remarkably improved the direct liquefaction effect of coal. Researcheres develop multiple method and prepare the Fe-series catalyst with higher catalytic activity. The preparation method that patent CN99103015.X discloses a kind of pulpous state highly-dispersed iron-base coal liquidation catalyst, iron salt solutions and ammonia react the unformed Fe of generation (OH)3Or Fe (OH)2Ultrafine particle, then the hydrogel formed after they centrifuge dehydrations is mixed and made into pulpous state ferrum-based catalyst with coal dust and liquefaction solvent. The preparation method that patent CN03153377.9 discloses a kind of high dispersive iron-based DCL/Direct coal liquefaction catalyst, impregnates coal dust with ferrous salt solution, obtains being loaded with Fe (OH) after adding alkali liquor2The coal slurry of precipitation, obtains the high dispersive DCL/Direct coal liquefaction catalyst of coal load γ-FeOOH with air or oxygen after aoxidizing. The preparation method that patent 201510373316.X discloses a kind of catalyst for coal liquefaction, with ferrous salt solution impregnated carbon particulate vector, adds aqueous slkali under passing into air or oxygen, obtains the alpha-feooh catalyst being carried on carbon granule. The preparation method that patent 200810302171.4 discloses a kind of catalyst for coal liquefaction being carrier with molecular sieve, molecular sieve carrier is immersed in ferrum, cobalt, nickel, one or more mixture of molybdenum saline solution, post-drying, in 200-800 degree air roasting obtain molecular sieve carried ferrum oxide, nickel oxide, cobalt oxide, molybdenum oxide catalyst.The preparation method that patent 201510435128.5 discloses a kind of Fe-series catalyst, reacts iron content soluble-salt and the aqueous solution containing manganese soluble-salt to prepared containing FeOOH and MnO (OH) with alkaline aqueous solution2Slurry, afterwards it is mixed with carrier materials such as coal dust, activated carbon, CNTs, after filtration, obtains ferrum system DCL/Direct coal liquefaction catalyst.
It can be seen that these loaded catalysts all demonstrate higher coal conversion ratio and distilled oil yield for DCL/Direct coal liquefaction reaction. But, in the preparation process of these catalyst, it is necessary to consume substantial amounts of water, and strictly controlling the pH value of reaction system, program is complicated, and this adds the preparation cost of Fe-series catalyst undoubtedly, limits its extensive use. Therefore, the simple and convenient process for preparing developing excellent DCL/Direct coal liquefaction Fe-series catalyst is very necessary.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of method preparing DCL/Direct coal liquefaction Fe-series catalyst. By using raw material cheap and easy to get, adopting easy operational approach, can prepare Ferrious material oxygen (hydrogen-oxygen) compound of load of producing coal through solid state reaction, this composite is used as DCL/Direct coal liquefaction catalysts, it demonstrates good catalytic effect.
Technical scheme is as follows:
At room temperature, the Ferrious material salt that mass ratio is 0.03 ~ 25:1 is mixed with coal dust, add alkali afterwards, the mol ratio of Ferrious material salt and alkali is 0.1 ~ 0.5:1, being ground or ball milling is to promote that solid state reaction occurs on coal dust for slaine and alkali, product is scrubbed, obtain the Fe-series catalyst for DCL/Direct coal liquefaction reaction after drying.
Coal dust of the present invention is the raw material coal dust for DCL/Direct coal liquefaction reaction or the coal dust after peracid treatment, described Ferrious material salt is one or both in ferric iron, ferrous iron, bivalence cobalt, the nitrate of nickelous, sulfate, acetate, chloride, and described alkali is sodium hydroxide or potassium hydroxide. By the step described in the method, it is possible to prepare Ferrious material oxygen (hydrogen-oxygen) compound for DCL/Direct coal liquefaction/coal composite Fe-series catalyst, including Fe3O4/ coal, Fe (OH)3/ coal, Co (OH)2/ coal, Ni (OH)2/ coal. In this iron series series catalysts, iron series element content is 1 ~ 60wt%.
It is that coal dust joins mass fraction is that the sulphuric acid of 10 ~ 80wt%, nitric acid, aqueous hydrochloric acid solution are in one or both with the method step of acid treatment coal dust, the solid-liquid mass ratio of coal dust and acid solution is 0.01 ~ 0.2:1, stirring, 20 ~ 80 degree of lower maintenances 3 ~ 48 hours, separate, dry obtain acid treated coal dust.
Compared with prior art, the invention have the advantages that based on solid state reaction, adopt raw material cheap and easy to get, by simply grinding or spheroidal graphite operation, coal loading type iron series catalysts can be prepared. In complex catalyst, active component iron system metal oxygen (hydrogen-oxygen) compound has reduced size, contacts well with coal carrier, and is evenly distributed on carrier, and this makes catalyst have higher catalytic activity, can effectively facilitate the conversion liquefaction of coal. When the coal dust of employing acid treatment is as carrier material, the functional group contained by its surface can promote active component formation on carrier and dispersion further. Preparation method is simple, and catalyst production is high, it is easy to accomplish the features such as production in enormous quantities all make the present invention have extremely wide application prospect.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated. These embodiments are interpreted as being merely to illustrate the present invention rather than limiting the scope of the invention. After having read the content that the present invention records, based on principles of the invention, the made various changes of the present invention or amendment are fallen into claims of the present invention limited range equally.
Embodiment 1
By 1.1g iron chloride (FeCl3·6H2O), 0.4g ferrous chloride (FeCl2·4H2O), 0.12g coal dust (Xinjiang Heishan coal, 200 orders) mixing, grind make it be sufficiently mixed, add 0.64g sodium hydroxide (NaOH) afterwards, continuing to grind and within about 0.5 hour, make them that solid state reaction occurs, products in water washs, and under 80 degree, forced air drying obtained Fe after 6 hours3O4/ coal complex catalyst.
Embodiment 2
Use sulfuric acid treatment coal dust, 5g coal dust (Xinjiang Heishan coal, 200 orders) is joined 450mL aqueous sulfuric acid (H2SO4Mass fraction is 32.7wt%) in, stirring reaction 24 hours under 20 degree, separate, dry obtain sulfuric acid-treated after coal dust; By 1.6 ferric nitrates (Fe (NO3)3·9H2O), 0.56g ferrous sulfate (FeSO4·7H2O), 0.48g coal dust (sulfuric acid-treated rear coal dust) mixing, grinding makes it be sufficiently mixed, and adds 0.64g sodium hydroxide (NaOH) afterwards, continues grinding and within about 0.5 hour, makes them that solid state reactions occur, products in water washs, and under 80 degree, forced air drying obtained Fe after 6 hours3O4/ coal complex catalyst.
Embodiment 3
By 11.7g iron chloride (Fe2(SO4)3·H2O), 12.8g coal dust (Xinjiang Heishan coal, 200 orders) mixing, ball milling makes it be sufficiently mixed, add 8.4g potassium hydroxide (KOH) afterwards, continuing ball milling makes them that solid state reaction occurs for about 0.5 hour, and products in water washs, and under 80 degree, forced air drying obtains Fe (OH) after 6 hours3/ coal complex catalyst.
Embodiment 4
By 24.9g cobaltous acetate (Co (CH3COO)2·4H2O), 9.3g coal dust (Xinjiang Heishan coal, 200 orders) mixing, grind make it be sufficiently mixed, add 8g sodium hydroxide (NaOH) afterwards, continuing to grind and within about 0.5 hour, make them that solid state reaction occurs, products in water washs, and under 80 degree, forced air drying obtains Co (OH) after 6 hours2/ coal complex catalyst.
Embodiment 5
By 2.4g Nickel dichloride. (NiCl2·2H2O), 0.9g coal dust (Xinjiang Heishan coal, 200 orders) mixing, grind make it be sufficiently mixed, add 0.8g sodium hydroxide (NaOH) afterwards, continuing to grind and within about 0.5 hour, make them that solid state reaction occurs, products in water washs, and under 80 degree, forced air drying obtains Ni (OH) after 6 hours2/ coal complex catalyst.
Comparative example 1
By 5.4g iron chloride (FeCl3·6H2O), 2g ferrous chloride (FeCl2·4H2O) mixing, grinds and makes it be sufficiently mixed, and adds 3.2g sodium hydroxide (NaOH) afterwards, continues grinding and within about 0.5 hour, makes them that solid state reaction occurs, and products in water washs, and under 80 degree, forced air drying obtained Fe after 6 hours3O4Catalyst.
The catalyst weighed respectively in a certain amount of embodiment 1,2 and comparative example 1 carries out DCL/Direct coal liquefaction experiment, and to evaluate their catalytic performance, test condition is as follows:
Xinjiang Heishan coal (200 order) is adopted to carry out DCL/Direct coal liquefaction reaction, loading type iron series catalysts is added in autoclave with 10g coal dust, 0.14g promoter sulfur powder, 20g liquefaction solvent naphthane, wherein adding the measurement criteria of catalyst be iron series element content is the 1.4wt% of coal dust, 6MPa hydrogen it is filled with in autoclave, react 1 hour at 430 degree, liquefaction products is stripped through Soxhlet extractor with normal hexane, toluene, oxolane respectively, calculating conversion ratio and the oil productivity of coal, result is in Table 1.
Table 1 DCL/Direct coal liquefaction result
| Catalyst | Conversion ratio/wt% | Oil productivity/wt% | Gas productivity/wt% | Asphaltene productivity/wt% | Preasphaltene productivity/wt% | Liquefied fraction/wt% |
| Embodiment 1 | 74.8 | 47.7 | 12.8 | 10.4 | 3.9 | 62.0 |
| Embodiment 2 | 86.1 | 62.2 | 14.7 | 7.2 | 2.0 | 71.4 |
| Comparative example 1 | 67.9 | 43.5 | 13.3 | 6.5 | 4.6 | 54.6 |
By the coal liquefaction result in table 1 it can be seen that iron series series catalysts of the present invention is in the less situation of addition, Xinjiang Heishan coal is liquefied, it is thus achieved that higher conversion ratio and oil productivity. Loaded catalyst obtained by embodiment 1,2 shows than the Fe obtained by comparative example 13O4Higher coal conversion ratio and oil productivity. In addition, it have been found that, during using the coal dust of acid treatment as carrier, complex catalyst (embodiment 2) shows the highest catalysis activity, this is likely due to the surface of coal dust to be made to contain more polyfunctional group with acid treatment coal dust, therefore active component is smaller, disperses reason evenly on carrier.
The invention provides the method for preparing solid phase of the loading type iron system DCL/Direct coal liquefaction catalyst with higher catalytic activity. The method does not use solvent, easy and simple to handle, mild condition, it is easy to industrialized mass.
Claims (5)
1. the method for preparing solid phase of a DCL/Direct coal liquefaction Fe-series catalyst, it comprises the following steps: at room temperature, coal dust is mixed with Ferrious material salt, add alkali afterwards, being ground or ball milling is to promote that solid state reaction occurs on coal dust for slaine and alkali, product is scrubbed, obtain the Fe-series catalyst for DCL/Direct coal liquefaction reaction after drying.
2. the method for preparing solid phase of a kind of DCL/Direct coal liquefaction Fe-series catalyst according to claim 1, it is characterised in that: the mass ratio of Ferrious material salt and coal dust is 0.03 ~ 25:1, and the mol ratio of Ferrious material salt and alkali is 0.1 ~ 0.5:1.
3. the method for preparing solid phase of a kind of DCL/Direct coal liquefaction Fe-series catalyst according to claim 1-2, it is characterized in that: the coal dust used is the raw material coal dust for DCL/Direct coal liquefaction reaction or the coal dust after peracid treatment, the Ferrious material salt used is one or both in ferric iron, ferrous iron, bivalence cobalt, the nitrate of nickelous, sulfate, acetate, chloride, and the alkali used is sodium hydroxide or potassium hydroxide.
4. the method for preparing solid phase of a kind of DCL/Direct coal liquefaction Fe-series catalyst according to claim 1-3, it is characterised in that: obtained Fe-series catalyst is Ferrious material oxygen (hydrogen-oxygen) compound/coal composite, including Fe3O4/ coal, Fe (OH)3/ coal, Co (OH)2/ coal, Ni (OH)2/ coal; In Fe-series catalyst, iron series element content is 1 ~ 60wt%.
5. the method for preparing solid phase of a kind of DCL/Direct coal liquefaction Fe-series catalyst according to claim 1-3, it is characterized in that: be that coal dust is joined in acid solution by the step of acid treatment coal dust, stirring, 20 ~ 80 degree lower maintenances 3 ~ 48 hours, separates, dries and obtain acid treated coal dust; The acid solution used is mass fraction is one or both in the sulphuric acid of 10 ~ 80wt%, nitric acid, aqueous hydrochloric acid solution; The solid-liquid mass ratio of coal dust and acid solution is 0.01 ~ 0.2:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799232A (en) * | 2016-12-15 | 2017-06-06 | 浙江工业大学 | Iron based ammonia synthesis catalyst of Nanoscale Iron modification prepared by a kind of solid state chemical reaction and its preparation method and application |
| CN107349948A (en) * | 2017-06-15 | 2017-11-17 | 华东理工大学 | A kind of iron alkali composite catalyst for DCL/Direct coal liquefaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853776A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Iron-based coal liquefied catalyst and production thereof |
| CN104826662A (en) * | 2015-05-06 | 2015-08-12 | 北京中科诚毅科技发展有限公司 | Iron catalyst for slurry reactor hydrogenation, preparation, design method, and applications thereof |
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- 2016-01-07 CN CN201610008686.8A patent/CN105664946B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853776A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Iron-based coal liquefied catalyst and production thereof |
| CN104826662A (en) * | 2015-05-06 | 2015-08-12 | 北京中科诚毅科技发展有限公司 | Iron catalyst for slurry reactor hydrogenation, preparation, design method, and applications thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106799232A (en) * | 2016-12-15 | 2017-06-06 | 浙江工业大学 | Iron based ammonia synthesis catalyst of Nanoscale Iron modification prepared by a kind of solid state chemical reaction and its preparation method and application |
| CN106799232B (en) * | 2016-12-15 | 2019-08-06 | 浙江工业大学 | A kind of iron based ammonia synthesis catalyst and its preparation method and application of the Nanoscale Iron modification of solid state chemical reaction preparation |
| CN107349948A (en) * | 2017-06-15 | 2017-11-17 | 华东理工大学 | A kind of iron alkali composite catalyst for DCL/Direct coal liquefaction |
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