CN1594508A - Method for application of waste iron base catalyst in hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon - Google Patents

Method for application of waste iron base catalyst in hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon Download PDF

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CN1594508A
CN1594508A CN 200410012386 CN200410012386A CN1594508A CN 1594508 A CN1594508 A CN 1594508A CN 200410012386 CN200410012386 CN 200410012386 CN 200410012386 A CN200410012386 A CN 200410012386A CN 1594508 A CN1594508 A CN 1594508A
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catalyst
fischer
hydrocracking
iron
heavy hydrocarbon
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CN100383221C (en
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任杰
李永旺
路风辉
董琳
王峰
李英
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Zhongke Synthetic Oil Technology Co Ltd
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The invention discloses a method for application of waste iron base catalyst in hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon characterized in that, waste ferrum based catalyst is mixed with heavy weight hydrocarbons for hydrocracking reaction, wherein the content of waste ferrum based catalyst is 0.1-10 wt%, the hydrocracking condition being, total pressure of suspending bed reactor 2.0-20.0MPa, temperature 370-500 deg. C, hydrogen / oil volume ratio 300-1500.

Description

The application method of iron content spent catalyst in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking
Technical field
The invention belongs to a kind of method that is used for the heavy hydrocarbon floating bed hydrocracking, relate in particular to the application method of a kind of iron content spent catalyst in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking.
Background technology
In the thick product of Fischer-Tropsch synthesis, have>30% for boiling point greater than 530 ℃ heavy hydrocarbon, this product does not have sulphur, no nitrogen, is mainly straight-chain paraffin and alkene, and oxycompound on a small quantity.Particularly, in the iron-based syrup state bed Fischer Tropsch building-up process, also have a large amount of heavy hydrocarbon (renaming as kettle bottom wax to show difference) and discharge when catalyst changeout more, this part kettle bottom wax also contains the catalyst based and colloid of a large amount of scrap iron except that boiling point is higher.Though kettle bottom wax is not high at whole Fischer-Tropsch synthetic proportion,, will promote Fischer-Tropsch synthetic comprehensive benefit greatly if can fully utilize.
USP4999328 has introduced a kind of dreg-oil suspension bed hydrogenation cracking catalyzer, to be crushed to broken coke button of 8~16 purposes and ferric sulfate, heavy oil mixing, three's ratio is 35: 15: 50, and the grinding machine of scoring then is milled to molysite and coke powder particle all less than 200 orders, and is most of less than 30 μ m.This catalyzer is used for floating bed hydrogenation, and as reaction pressure 13.9MPa, asphalt quality transformation efficiency during 450 ℃ of temperature (basic noncoking) can reach 88%.The coke button at least 1% of impregnation iron 10% (to charging) in the charging.This process reaction pressure height, the add-on of catalyzer big (about 1wt%), and also catalyzer is disposable passes through, and makes that overall cost is higher.
CN1162621A has introduced a kind of water-soluble hydrocracking catalyst for suspension bed, and molybdenum oxide and basic nickel carbonate are joined in the phosphate aqueous solution, forms aqueous catalyst solution.Wherein molybdenum content is 6~8wt%; Nickel content is 0.3~0.8wt%; Phosphorus content is 0.2~0.4wt%.Then aqueous catalyst solution is distributed in weight, the residual oil raw material, forms milk sap, enter reactor then.In the 750ml autoclave reactor, the total metal add-on 250 μ g/g of catalyzer, reaction pressure 7Mpa is during 440 ℃ of temperature, about<500 ℃ of product yield 75wt%, wherein<350 about ℃ product yield 45wt%.This invention is when being applied to scale operation, and the water-soluble catalyst consumption can be very big, and is not recyclable, and emulsification needs special equipment in the process, makes that overall cost is higher.
Summary of the invention
The purpose of this invention is to provide the catalyst based floating bed hydrocracking application method of a kind of scrap iron with low cost, that transformation efficiency is high and selectivity is high.
Ferrum-based catalyst has hydrocracking effect preferably to Fischer-Tropsch synthesis of heavy hydrocarbon, and particularly to wherein contained oxygenatedchemicals, effect is better.Contained useless Fischer-Tropsch synthetic iron-based catalyst in the kettle bottom wax though catalysis Fischer-Tropsch composite reactive is very low, also has higher hydrogenation activity, and suitable cracking activity, and physical strength is more suitable to hydrocracking catalyst for suspension bed than higher.If be used with other hydrocracking catalyst for suspension bed, its hydrocracking effect is better.Comprise that scrap iron in the catalyst based and carbon monodixe conversion process of the scrap iron in the synthetic ammonia process is catalyst based etc. and other scrap iron is catalyst based, in experimentation, all shown hydrocracking effect preferably.
Application method of the present invention comprises the steps:
The catalyst based mixing with Fischer-Tropsch synthesis of heavy hydrocarbon of scrap iron carried out hydrocracking reaction, and wherein the catalyst based add-on of scrap iron is 0.1wt ‰~10wt%, is preferably 1wt ‰~5wt%, and the best is 1wt ‰~2.5wt%.The hydrocracking process condition is: the suspended-bed reactor total pressure is 2.0~20.0Mpa, 370~500 ℃ of temperature, and hydrogen/oil volume is than 300~1500.
Aforesaid scrap iron is catalyst based can also to be used from the Fischer-Tropsch synthesis of heavy hydrocarbon floating bed hydrocracking with hydrocracking catalyst for suspension bed one.Improve liquid fuel oil yield and selectivity by adding a spot of other hydrocracking catalyst for suspension bed.
Aforesaid hydrocracking catalyst for suspension bed is the hydrocracking catalyst for suspension bed of iron-based.
The catalyst based wherein iron level 〉=40wt% of aforesaid scrap iron.
The scrap iron that aforesaid scrap iron is catalyst based to comprise that the scrap iron that displaces in the Fischer-Tropsch building-up process is catalyst based, displace in the synthetic ammonia process is catalyst based, and the scrap iron that displaces in the carbon monodixe conversion process is catalyst based etc.
The scrap iron that displaces in the aforesaid Fischer-Tropsch building-up process is catalyst based, arrives the spent catalyst that work-ing life, postposition swapped out as the iron-base fischer-tropsch synthesis catalyst of mentioning among patent CN01120416, CN1113905A, CN01120417.6, USP5324335, USP5504118, USP6716790, the WO99/49965 etc.
The scrap iron that displaces in the aforesaid synthetic ammonia process is catalyst based, arrives the spent catalyst that work-ing life, postposition swapped out as synthetic ammonia catalysts such as A103H, A203, HA202Q, HA203Q, HA310Q, HA202W, HA203W, HA310W, A110MQ, A110MW, A301, AMOMX-10, AMOMX-10H.
The scrap iron that displaces in the aforesaid carbon monodixe conversion process is catalyst based, arrives the spent catalyst that work-ing life, postposition swapped out as the iron-based carbon monoxide transformation catalyst of mentioning among CN90101486.9, CN90100424.3, CN90109829.9, CN92103818.6, CN92111123.1, CN94113013.4, CN95121834.4, CN96102477.1, CN98124006.2, CN00105435.x, CN01138010.1, the CN02137964.5 etc.
Characteristics of the present invention are as follows:
1. it is catalyst based that the present invention can make full use of various scrap iron, has environment protecting preferably.
2. the inventive method is easy, and catalyzer once passes through, easily operation.
3. catalyst aims Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking process of suspended bed of the present invention has higher activity and intermediate oil selectivity.
4. it is catalyst based that the present invention utilizes various scrap iron, particularly utilizes scrap iron base fischer-tropsch synthetic catalyst as the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking catalyst for suspension bed, improved iron-based syrup state bed Fischer Tropsch synthetic overall economic efficiency greatly.
Embodiment
The following examples will the present invention is described further, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Embodiment 1
Use that the scrap iron that displaces in the Fischer-Tropsch building-up process of the microsphere shaped iron based catalyst that CN 01120416 mentions is catalyst based to be hydrocracking catalyst for suspension bed, iron level 78wt% wherein, with the Fischer-Tropsch synthesis of heavy hydrocarbon is raw material, the catalyst based add-on 5wt% of scrap iron, at reaction pressure 4.0Mpa, hydrogen-oil ratio 1200, under 440 ℃ of the temperature, estimate, the calculating of intermediate oil selectivity obtains by " ratios of (boat yield of coal+diesel yield) and<370 ℃ of product yields ", the results are shown in Table 1.
Embodiment 2
Use that the scrap iron that displaces in the Fischer-Tropsch building-up process of the ferrum-based catalyst that CN1113905A mentions is catalyst based to be hydrocracking catalyst for suspension bed, iron level 70wt% wherein, the catalyzer add-on is 10wt%, at reaction pressure 2.0Mpa, hydrogen-oil ratio 1500, under 380 ℃ of the temperature, estimate, the results are shown in Table 1.
Embodiment 3
Use that the scrap iron that displaces in the Fischer-Tropsch building-up process of the ferrum-based catalyst that WO99/49965 mentions is catalyst based to be hydrocracking catalyst for suspension bed, iron level 73wt% wherein, the catalyzer add-on is 4wt%, at reaction pressure 7.0Mpa, hydrogen-oil ratio 1000, under 460 ℃ of the temperature, estimate, the results are shown in Table 1.
Embodiment 4
Use that the scrap iron that displaces in the carbon monodixe conversion process of the ferrum-based catalyst that CN92111123.1 mentions is catalyst based to be hydrocracking catalyst for suspension bed, iron level 67wt% wherein, add-on 0.7wt%, at reaction pressure 15Mpa, hydrogen-oil ratio 500, under 470 ℃ of the temperature, estimate, the results are shown in Table 1.
Embodiment 5
Use that the scrap iron that displaces in the carbon monodixe conversion process of the ferrum-based catalyst that CN90109829.9 mentions is catalyst based to be hydrocracking catalyst for suspension bed, iron level 65wt% wherein, add-on 0.2wt%, at reaction pressure 20.0Mpa, hydrogen-oil ratio 300, under 490 ℃ of the temperature, estimate, the results are shown in Table 1.
Embodiment 6
Use that the scrap iron that displaces in the carbon monodixe conversion process of the ferrum-based catalyst that CN98124006.2 mentions is catalyst based to be hydrocracking catalyst for suspension bed, iron level 69wt% wherein, add-on 2wt%, at reaction pressure 12Mpa, hydrogen-oil ratio 500, under 450 ℃ of the temperature, estimate, the results are shown in Table 1.
Embodiment 7
Use that the scrap iron that displaces in the synthetic ammonia process of A103H catalyzer is catalyst based to be hydrocracking catalyst for suspension bed, iron level 81wt% wherein, add-on 1wt%, at reaction pressure 6.0Mpa, hydrogen-oil ratio 800 is under 430 ℃ of the temperature, estimate, the results are shown in Table 1.
Embodiment 8
Use that the scrap iron that displaces in the synthetic ammonia process of HA202W catalyzer is catalyst based to be hydrocracking catalyst for suspension bed, iron level 83wt% wherein, add-on 7wt%, at reaction pressure 8.0Mpa, hydrogen-oil ratio 800 is under 400 ℃ of the temperature, estimate, the results are shown in Table 1.
Embodiment 9
Use that the scrap iron that displaces in the synthetic ammonia process of AMOMX-10 catalyzer is catalyst based to be hydrocracking catalyst for suspension bed, iron level 79wt% wherein, add-on 0.5wt%, add catalyst compounded iron nitrate 20wt%, the ammonium molybdate 20wt% of wherein containing of the water-soluble iron-based of mentioning among the CN01109276.9 again, add-on 0.005wt% is at reaction pressure 3.0Mpa, hydrogen-oil ratio 800, under 420 ℃ of the temperature, estimate, the results are shown in Table 1.
From table 1 data, the scrap iron of iron level 〉=40wt% is catalyst based, is used for the Fischer-Tropsch synthesis of heavy hydrocarbon floating bed hydrocracking and has higher transformation efficiency and intermediate oil selectivity.
The evaluation result of table 1 embodiment
Numbering per pass conversion (%) intermediate oil selectivity (%)
Embodiment 1 75.1 84.2
Embodiment 2 70.8 79.5
Embodiment 3 82.8 75.3
Embodiment 4 80.6 78.5
Embodiment 5 83.2 70.0
Embodiment 6 77.6 80.6
Embodiment 7 74.2 79.4
Embodiment 8 70.1 82.7
Embodiment 9 74.6 80.4

Claims (10)

1, the application method of a kind of iron content spent catalyst in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking is characterized in that comprising the steps:
The catalyst based mixing with Fischer-Tropsch synthesis of heavy hydrocarbon of scrap iron carried out hydrocracking reaction, wherein the catalyst based add-on of scrap iron is 0.1wt ‰~10wt%, the hydrocracking process condition is: the suspended-bed reactor total pressure is 2.0~20.0Mpa, 370~500 ℃ of temperature, hydrogen/oil volume is than 300~1500.
2, the application method of a kind of iron content spent catalyst as claimed in claim 1 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking, it is characterized in that described scrap iron catalyst based can also and hydrocracking catalyst for suspension bed one be used from the Fischer-Tropsch synthesis of heavy hydrocarbon floating bed hydrocracking.
3, the application method of a kind of iron content spent catalyst as claimed in claim 1 or 2 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking is characterized in that the catalyst based add-on of scrap iron is 1wt ‰~5wt%.
4, the application method of a kind of iron content spent catalyst as claimed in claim 1 or 2 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking is characterized in that the catalyst based add-on of scrap iron is 1wt ‰~2.5wt%.
5, the application method of a kind of iron content spent catalyst as claimed in claim 1 or 2 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking is characterized in that the catalyst based wherein iron level 〉=40wt% of described scrap iron.
6, the application method of a kind of iron content spent catalyst as claimed in claim 2 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking is characterized in that described hydrocracking catalyst for suspension bed is the hydrocracking catalyst for suspension bed of iron-based.
7, the application method of a kind of iron content spent catalyst as claimed in claim 1 or 2 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking, the scrap iron that displaces in the catalyst based or carbon monodixe conversion process of the scrap iron that it is characterized in that described scrap iron catalyst basedly comprises that the scrap iron that displaces in the Fischer-Tropsch building-up process is catalyst based, displaces in the synthetic ammonia process is catalyst based.
8, the application method of a kind of iron content spent catalyst as claimed in claim 7 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking, it is characterized in that the scrap iron that displaces in the described Fischer-Tropsch building-up process catalyst based be that iron-base fischer-tropsch synthesis catalyst among patent CN01120416, CN1113905A, CN01120417.6, USP5324335, USP5504118, USP6716790 or the WO99/49965 arrives the spent catalyst that work-ing life, postposition swapped out.
9, the application method of a kind of iron content spent catalyst as claimed in claim 7 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking is characterized in that the catalyst based A103H of being of the scrap iron that displaces in the described synthetic ammonia process, A203, HA202Q, HA203Q, HA310Q, HA202W, HA203W, HA310W, A110MQ, A110MW, A301, AMOMX-10 or AMOMX-10H synthetic ammonia catalyst arrive the spent catalyst that work-ing life, postposition swapped out.
10, the application method of a kind of iron content spent catalyst as claimed in claim 7 in the Fischer-Tropsch synthesis of heavy hydrocarbon hydrocracking is characterized in that the catalyst based CN90101486.9 of being of scrap iron that displaces in the described carbon monodixe conversion process, CN90100424.3, CN90109829.9, CN92103818.6, CN92111123.1, CN94113013.4, CN95121834.4, CN96102477.1, CN98124006.2, CN00105435.x, the iron-based carbon monoxide transformation catalyst of mentioning among CN01138010.1 or the CN02137964.5 arrives the spent catalyst that work-ing life, postposition swapped out.
CNB2004100123864A 2004-07-06 2004-07-06 Method for application of waste iron base catalyst in hydrocracking of Fischer-Tropsch synthesized heavy hydrocarbon Expired - Lifetime CN100383221C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103289722A (en) * 2013-06-08 2013-09-11 神华集团有限责任公司 Recycling method of iron-based waste catalyst for Fischer-Tropsch synthesis and direct coal liquefaction reaction catalyst
US10563130B2 (en) 2014-07-17 2020-02-18 Sabic Global Technologies B.V. Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4344840A (en) * 1981-02-09 1982-08-17 Hydrocarbon Research, Inc. Hydrocracking and hydrotreating shale oil in multiple catalytic reactors
CN1050151C (en) * 1997-12-23 2000-03-08 石油大学(华东) Cataluyst for slag oil suspension bed hydrogen cracking
CN1073618C (en) * 1998-11-18 2001-10-24 中国石油化工集团公司 Heavy hydrocarbons hydrocraking catalyst and its preparation and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103289722A (en) * 2013-06-08 2013-09-11 神华集团有限责任公司 Recycling method of iron-based waste catalyst for Fischer-Tropsch synthesis and direct coal liquefaction reaction catalyst
CN103289722B (en) * 2013-06-08 2015-06-17 神华集团有限责任公司 Recycling method of iron-based waste catalyst for Fischer-Tropsch synthesis and direct coal liquefaction reaction catalyst
US10563130B2 (en) 2014-07-17 2020-02-18 Sabic Global Technologies B.V. Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process

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