CN101225335A - Water coke slurry for gasification and preparation method thereof - Google Patents
Water coke slurry for gasification and preparation method thereof Download PDFInfo
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- CN101225335A CN101225335A CNA200810017478XA CN200810017478A CN101225335A CN 101225335 A CN101225335 A CN 101225335A CN A200810017478X A CNA200810017478X A CN A200810017478XA CN 200810017478 A CN200810017478 A CN 200810017478A CN 101225335 A CN101225335 A CN 101225335A
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Abstract
The invention relates to water-coke slurry and the preparation method, in particular to a water-coke slurry for gasification with refinery coke as the material and the preparation method, which is characterized in that: the material compositions (mass percentages) are refinery coke of 60 to 80%, dispersing agent of 0.5 to 5% and water of 20 to 39.5%; the steps of the preparation method are as follows: the refinery coke is first broken up to less than 5mm, and then the broken refinery coke is divided into two parts, and the two parts are respectively grinded together with quantitative dispersing agent and water in two grinders; by adjusting the stick-coke ratio of two grinders, the water-coke slurries output from the two grinders have different granularity distributions, and the two water-coke slurries are mixed to obtain the water-coke slurry for gasification; when the viscosity is about 1000mPas, the concentration of the refinery coke in the water-coke slurry can be increased to 72%. The water-coke slurry has the advantages of legitimately utilizing the lignin-sulphonate industrial waste and changing waste into valuable, as well as preparing high-quality water-coke slurry for gasification, and having good fluidity and stability.
Description
Technical field:
The present invention relates generally to burnt slurry of water and preparation method thereof, and relating in particular to the refinery coke is water coke slurry for gasification of raw material and preparation method thereof.
Background technology:
Refinery coke is the product of various residual oil, heavy oil delayed coking.Refinery coke is mainly used in the fuel of Cement industry kiln, plain cylindrical furnace and circulating fluidized bed at present.Along with the heaviness and poor qualityization of crude oil, refinery coke is as the final product of petroleum refining, and output significantly increases.How rationally to utilize refinery coke, especially high sulfur petroleum coke to become a urgent problem.
With the refinery coke is raw material production synthetic gas (CO+H
2) be the effective way that refinery coke utilizes, and refinery coke just continues to increase as the proportion of gasified raw material.Studies show that between the five-year that refinery coke is as one of gasified raw material, will from 2004 3% rise to 8%.The slurry charging is a kind of main mode of gasification, how to prepare the burnt slurry of the water that is fit to gasification usefulness and has important and practical meanings.
The carbon content height of refinery coke, oxy radical is few, thereby particle surface has very strong hydrophobicity, and the burnt slurry of the water of preparation high density, good rheological has bigger difficulty.The domestic patent report (CN1275610A, CN 1127558C) that has only refinery coke and coal mixed pulp.JP 57168995 has reported a kind of burnt slurry of water preparation method who adopts the ether dispersion agent, but the dispersion agent preparation is complicated, and cost is higher.
Summary of the invention:
The objective of the invention is to avoid the deficiencies in the prior art part and a kind of water coke slurry for gasification and preparation method thereof is provided, to the surface properties of refinery coke, contained group, grain breakage kinetics, with the basis of the The effect such as effect of dispersion agent on, the industrial waste that the present invention adopts sulfonated lignin and contains sulfonated lignin is as burnt slurry of water of dispersion agent and preparation method thereof.The burnt slurry of the water of preparation has higher density of petroleum coke, and good is mobile and stable, meets the requirement of gasification with slurry.
Purpose of the present invention can be by realizing by the following technical solutions: a kind of water coke slurry for gasification, it is the 60-80% refinery coke that its raw material is formed (mass percent), 0.5%-5% dispersion agent, 20-39.5% water.
Described water coke slurry for gasification, described dispersion agent are sulfonated lignin or the industrial waste that contains sulfonated lignin.This industrial waste low price, the source is abundant.Wherein contain a large amount of surfactant materials, possess good dispersiveness and stable simultaneously.This mechanism of dispersants is: the SURFACTANT ADSORPTION in the dispersion agent forms very thin additive molecule and the hydration shell of one deck on the petroleum coke particles surface, reduces the interfacial tension between particle and the water greatly.At this moment, the particle in the suspension is good dispersion state, is separated from each other between particle, and the particle outside surface also has the firm hydration shell of one deck, does not produce new phase interface during shearing, and the shearing stress of generation reduces, and promptly viscosity reduces.
The preparation method of described water coke slurry for gasification, described refinery coke is a green coke, and carbon content is 85-92%, and ash content is 0.10-0.80%, and volatilization is divided into 5.0-12%.
The preparation method of described water coke slurry for gasification includes following steps:
1) earlier the 60-80% refinery coke is crushed to＜5mm;
2) refinery coke after the fragmentation is ground, carries out the preparation of burnt slurry of thin water and the burnt slurry of thick water:
The preparation of the burnt slurry of a. thin water: dispersion agent and the 20-39.5% water with 0.5-5% in grinding machine of the refinery coke after the fragmentation is ground, the grinding particle diameter of the burnt slurry of thin water is 20-25 μ m, viscosity is 1786-2492mPas when shearing rate is 100s-1, and static stability hard-caked sediment do not occur for leaving standstill 80-90h;
The preparation of the burnt slurry of b. thick water: dispersion agent and the 20-39.5% water with 0.5-5% in grinding machine of the refinery coke after the fragmentation is ground, the grinding particle diameter of the burnt slurry of thick water is 80-90 μ m, viscosity is 1212-1532mPas when shearing rate is 100s-1, and static stability hard-caked sediment do not occur for leaving standstill 15-20h;
3) above-mentioned thin water Jiao slurry and thick water Jiao are starched with 5-8: the 3-6 ratio is mixed, thereby makes water coke slurry for gasification.
The burnt slurry of water mean particle size 30-100 μ m, viscosity＜1150mPas, 24h static state deposition rate＜5%.The burnt slurry of the water of preparation has higher density of petroleum coke, and good is mobile and stable, meets the requirement of gasification with slurry.
Illustrate:
1. the viscosity when viscosity is meant 100s-1, fixed with NXS-4C type viscosity in aqueous coal slurries instrumentation;
2. bleed rate and deposition rate all are meant 24h bleed rate and static state deposition rate, measure by static stability measuring method among the GB GB/T 18856.4-2002.
The invention has the beneficial effects as follows, rationally utilize the sulfonated lignin industrial waste on the one hand, turn waste into wealth; Can prepare high-quality water coke slurry for gasification on the other hand.During the viscosity 1000mPas left and right sides, the burnt slurry of water Jiao's of PetroChina Company Limited. concentration can bring up to 72%, has good flowability and stable simultaneously.Adopt and grind earlier the burnt slurry of water that the water coal/Jiao's slurry preparation method who afterwards joins obtains having the fine granularity distribution.
Description of drawings:
Fig. 1 is the character figure of the burnt slurry of 1 two kinds of water of the embodiment of the invention;
Fig. 2 is the character figure of the burnt slurry of 2 two kinds of water of the embodiment of the invention.
Embodiment:
Be described in further detail below in conjunction with most preferred embodiment, the present invention is further illustrated, but the present invention is not limited to following examples.
The refinery coke of following examples is a green coke, and carbon content is 85-92%, and ash content is 0.10-0.80%, and volatilization is divided into 5.0-12%.Analytical data is as follows:
The technical analysis of table 1 refinery coke and ultimate analysis
| Sample | Technical analysis | Ultimate analysis | |||||||
| M ad | A ad | V ad | FC ad | C | H | N | S | | |
| Refinery coke | |||||||||
| 1 refinery coke 2 | 0.79 0.64 | 0.56 0.21 | 10.04 10.03 | 88.61 89.12 | 90.25 89.96 | 3.745 3.669 | 1.736 1.510 | 3.028 3.847 | 1.241 1.014 |
The 60-80% refinery coke, 0.5%-5% dispersion agent, 20-39.5% water.
Embodiment 1:
Water coke slurry for gasification, it is 60% refinery coke that its raw material is formed (mass percent), 0.5% dispersion agent and 39.5% water, dispersion agent is for containing sulfonated lignin.
Embodiment 2:
Water coke slurry for gasification, it is 75% refinery coke that its raw material is formed (mass percent), 5% dispersion agent, 20% water, dispersion agent is for containing sulfonated lignin.
Embodiment 3:
Water coke slurry for gasification, it is 65% refinery coke that its raw material is formed (mass percent), 2.5% dispersion agent, 32.5% water.Dispersion agent is the industrial waste that contains sulfonated lignin.
Embodiment 4:
Water coke slurry for gasification, it is 79.5% refinery coke that its raw material is formed (mass percent), 0.5% dispersion agent, 20% water, dispersion agent are the industrial waste that contains sulfonated lignin.
Embodiment 5:
The preparation method of water coke slurry for gasification, use refinery coke 1, refinery coke is crushed to＜5mm earlier, it is 60% refinery coke that its raw material is formed (mass percent), 0.5% dispersion agent and 39.5% water, dispersion agent is sulfonated lignin, with the refinery coke separated into two parts after the fragmentation, obtains the burnt slurry of water of thick, thin two kinds of size-grade distribution after grinding in two grinding machines.The two kinds of burnt slurry of water raw materials are formed identical.The character of the burnt slurry of two kinds of water are as shown in Figure 1: wherein, the median size of the burnt slurry of thin water is 22 μ m, and shearing rate is 100s
-1The time viscosity be 2492mPas, static stability hard-caked sediment do not occur for leaving standstill 80h; The median size of the burnt slurry of thick water is 87 μ m, and shearing rate is 100s
-1The time viscosity be 1532mPas, static stability hard-caked sediment do not occur for leaving standstill 20h.After the burnt slurry of thick, thin two kinds of water is mixed by different ratios, complementary effect occurs, promptly the viscosity degradation of the burnt slurry of water, stability rise.And slightly: be 7: 3 o'clock carefully, the burnt slurry of the water that obtains has minimum viscosity and the longest steady time.
Embodiment 6:
The preparation method of water coke slurry for gasification uses refinery coke 2, refinery coke is crushed to＜5mm earlier, and 75% refinery coke, 5% dispersion agent, 20% water, dispersion agent is for containing sulfonated lignin.With the refinery coke separated into two parts after the fragmentation, obtain the burnt slurry of water of thick, thin two kinds of size-grade distribution after in two grinding machines, grinding.The burnt slurry of two kinds of water raw material is formed identical, the character of two kinds of burnt slurries of water as shown in Figure 2: wherein, the median size of the burnt slurry of thin water is 20 μ m, and shearing rate is 100s
-1The time viscosity be 1786mPas, static stability hard-caked sediment do not occur for leaving standstill 88h; The median size of the burnt slurry of thick water is 98 μ m, and shearing rate is 100s
-1The time viscosity be 1212mPas, static stability hard-caked sediment do not occur for leaving standstill 16h.After the burnt slurry of thick, thin two kinds of water is mixed by different ratios, complementary effect occurs, promptly the viscosity degradation of the burnt slurry of water, stability rise.And slightly: be 6: 4 o'clock carefully, the burnt slurry of the water that obtains has minimum viscosity and the longest steady time.
Claims (4)
1. a water coke slurry for gasification is characterized in that it is the 60-80% refinery coke that its raw material is formed (mass percent), 0.5-5% dispersion agent, 20-39.5% water.
2. water coke slurry for gasification as claimed in claim 1 is characterized in that described dispersion agent is sulfonated lignin or the industrial waste that contains sulfonated lignin.
3. the preparation method of water coke slurry for gasification as claimed in claim 1 or 2 is characterized in that described refinery coke is a green coke, and carbon content is 85-92%, and ash content is 0.10-0.80%, and volatilization is divided into 5.0-12%.
4. the preparation method of water coke slurry for gasification as claimed in claim 1 is characterized in that including following steps:
1) earlier the 60-80% refinery coke is crushed to＜5mm;
2) refinery coke after the fragmentation is ground, carries out the preparation of burnt slurry of thin water and the burnt slurry of thick water:
The preparation of the burnt slurry of a. thin water: dispersion agent and the 20-39.5% water with 0.5-5% in grinding machine of the refinery coke after the fragmentation is ground, the grinding particle diameter of the burnt slurry of thin water is 20-25 μ m, viscosity is 1786-2492mPas when shearing rate is 100s-1, and static stability hard-caked sediment do not occur for leaving standstill 80-90h;
The preparation of the burnt slurry of b. thick water: dispersion agent and the 20-39.5% water with 0.5-5% in grinding machine of the refinery coke after the fragmentation is ground, the grinding particle diameter of the burnt slurry of thick water is 80-90 μ m, viscosity is 1212-1532mPas when shearing rate is 100s, and static stability hard-caked sediment do not occur for leaving standstill 15-20h;
3) above-mentioned thin water Jiao slurry and thick water Jiao are starched with 5-8: the 3-6 ratio is mixed, thereby makes water coke slurry for gasification.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886005A (en) * | 2010-07-26 | 2010-11-17 | 山东科技大学 | Method for preparing water coke slurry fuel by using oily water |
| CN102399605A (en) * | 2011-09-30 | 2012-04-04 | 惠生工程（中国）有限公司 | High-ash-fusion-point petroleum coke slurry used for gasification, and preparation method thereof |
| CN102899111A (en) * | 2012-11-01 | 2013-01-30 | 西北化工研究院 | Method for preparing gasified slurry from industrial effluent and coke powder |
| CN104651003A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Sludge coke slurry and preparation method thereof |
| US10287522B2 (en) | 2013-01-31 | 2019-05-14 | General Electric Company | System and method for preparing coal water slurry |
| CN113789195A (en) * | 2021-09-16 | 2021-12-14 | 浙江石油化工有限公司 | Safe and effective utilization method of high-sulfur petroleum coke slurry |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1127558C (en) * | 2000-08-25 | 2003-11-12 | 化学工业部西北化工研究院 | Process for preparing coke-water slurry to generate gas |
| CN100556996C (en) * | 2006-04-24 | 2009-11-04 | 广州迪森热能技术股份有限公司 | Desulfurized hydrated coking slurry formula and preparation technology thereof |
| CN101054541B (en) * | 2007-04-26 | 2010-11-24 | 华东理工大学 | Sludge petroleum charred slurry and preparing process and application thereof |
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2008
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101886005A (en) * | 2010-07-26 | 2010-11-17 | 山东科技大学 | Method for preparing water coke slurry fuel by using oily water |
| CN102399605A (en) * | 2011-09-30 | 2012-04-04 | 惠生工程（中国）有限公司 | High-ash-fusion-point petroleum coke slurry used for gasification, and preparation method thereof |
| CN102399605B (en) * | 2011-09-30 | 2014-04-30 | 惠生工程（中国）有限公司 | High-ash-fusion-point petroleum coke slurry used for gasification, and preparation method thereof |
| CN102899111A (en) * | 2012-11-01 | 2013-01-30 | 西北化工研究院 | Method for preparing gasified slurry from industrial effluent and coke powder |
| CN102899111B (en) * | 2012-11-01 | 2015-12-09 | 西北化工研究院 | A kind of method being produced gasification slip by trade effluent and coke powder |
| US10287522B2 (en) | 2013-01-31 | 2019-05-14 | General Electric Company | System and method for preparing coal water slurry |
| CN104651003A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Sludge coke slurry and preparation method thereof |
| CN113789195A (en) * | 2021-09-16 | 2021-12-14 | 浙江石油化工有限公司 | Safe and effective utilization method of high-sulfur petroleum coke slurry |
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Owner name: SINOPEC NINGBO TECHNOLOGY RESEARCH INSTITUTION CO. Free format text: FORMER OWNER: EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY SINOPEC NINGBO INSTITUTE OF TECHNOLOGY SINOPEC NINGBO ENGINEERING CO., LTD. Effective date: 20121225 Owner name: EAST CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY Free format text: FORMER OWNER: SINOPEC GROUP Effective date: 20121225 |
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Effective date of registration: 20121225 Address after: 200237 Meilong Road, Shanghai, No. 130, No. Patentee after: East China University of Science and Technology Patentee after: SINOPEC Ningbo Technology Research Institute Co., Ltd. Patentee after: SINOPEC Ningbo Engineering Company Limited Address before: 100029 Beijing City, Chaoyang District Hui Street No. 6 Patentee before: China Petrochemical Group Corp. Patentee before: East China University of Science and Technology Patentee before: Sinopec Ningbo Institute of Technology Patentee before: Sinopec Ningbo Engineering Co., Ltd. |