CN1197836A - Preparation process of water fluid fuel with solid carbon - Google Patents

Preparation process of water fluid fuel with solid carbon Download PDF

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Publication number
CN1197836A
CN1197836A CN 97103965 CN97103965A CN1197836A CN 1197836 A CN1197836 A CN 1197836A CN 97103965 CN97103965 CN 97103965 CN 97103965 A CN97103965 A CN 97103965A CN 1197836 A CN1197836 A CN 1197836A
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water
pitch
slurries
add
dispersion agent
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CN 97103965
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CN1054394C (en
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黄伟祈
龙军
祖德光
彭朴
史光伟
杨钧
李首先
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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Abstract

The present invention features its two-stage parallet wet grinding technology, i.e., solid petroleum asphalt and/or petroleum coke after grinding flows into two parallel ball mills, where dispersant and water are added to result in two kinds of slurry with different size, and the two kinds of slurry are then mixed, added with stabilizer and stirred to produce aquous slurry of 55-70% concentration. The present invention is simple in process and can produce aqueous slurry with good fluidity and viscosity below 1 Pa.s.

Description

A kind of method for preparing water fluid fuel with solid carbon
The invention belongs to the method for preparing water fluid fuel with solid carbon, more particularly, the present invention is to be raw material with carbon element solid materials such as petroleum pitch, petroleum coke, adds additive and water again and makes water slurry as fuel.
The heavy oil upgrading of petroleum refining industry is the heavy in the crude oil partly to be converted into light-end productss such as gasoline, kerosene, diesel oil, but also produces the by product that some are difficult to handle simultaneously inevitably.For example for more catalytically cracked material is provided, need to improve the extracting degree of depth of solvent deasphalting, but the bituminous quality will variation, produces more gilsonite, these gilsonite can not be as petroleum asphalt product.If act as a fuel, then need to call in a large amount of dilution light oil, this is very uneconomic.Delay coking process and for example, but except producing a spot of needle coke calcined coke, major part then is other coke of fuel-grade that is difficult to handle.Therefore how rationally utilizing these by products is exactly a very important problem.
In recent years, develop a kind of gilsonite aqueous slurry fluid fuel, it can also be used as ammonia raw material (and can further be used for hydrogen manufacturing, generating etc.) except the fuel that can be used as Industrial Boiler and Industrial Stoves.The method that proposes in the Japanese kokai publication sho 60-206898 patent application is earlier pitch to be made the rarer slurries of concentration, concentrates then to make concentration up to 65~75% slurries.This method need be acquired thickening equipment because concentration process is arranged, and has increased investment, process cost and the energy consumption of slurrying.Chinese patent application CN85106713A proposes dry grinding combines the system coal water slurry with wet grinding technology; with the dry grinding method coal is processed into coarse particles below 40 orders; grind the fine particle of particle size below 200 orders with wet milling process; to do wet two kinds of particles then mixes; and after in suitable technical process, adding dispersion agents such as polyethylene oxide derivatives, soap class, poly-second diimine, sulfonated lignin, finally make concentration in the coal water slurry more than 60%.To the coal dust after pulverizing be sieved earlier during this method dry grinding, dust from flying during screening, environmental pollution is serious, and particle influences screening efficiency easily with clogging of screen; On the other hand, when the dry/wet coal powder mixed, dry powder was difficult to by water-wet, caused transport pipe to stop up easily.In addition, the slurry viscosity that the dispersion agent that uses in these prior arts makes is bigger, have up to several thousand centipoises.
The objective of the invention is to overcome the shortcoming of prior art, the water slurry method of the preparation carbon element solid materials that a kind of flow process is simple, environmental pollution is little is provided.
Main technical schemes of the present invention: the technology that adopts two sections wet grindings in parallel, solid materials after being about to grind also flows in two ball mills, and the while adds dispersion agent and water in ball mill, to obtain two kinds of slurries that contain variable grain, these two kinds of slurries are mixed and add stablizer, can obtain the water slurry of desired concn through abundant stirring.
Concrete preparation process of the present invention is followed successively by:
1, the carbon element solid materials is ground to less than behind 40 orders, and flows to rough grinding machine and fine grinder and while adding dispersion agent and water in two shredders, rough grinding machine linear velocity is 1~1.5 meter per second, obtains containing 150~250 order particulate slurries; The fine grinder linear velocity is 1.5~2.0 meter per seconds, obtains containing 200~250 order particulate slurries.The add-on of dispersion agent and water is respectively the 0.1~5.0m% and the 43~82m% of solid materials amount.
2, two kinds of slurries that the 1st step was obtained mix and add stablizer, can obtain the water slurry product that concentration is following particle>75% of 55~70% and 200 orders through abundant stirring, the ratio of mixture of two kinds of slurries is 2~3: 3~2, the add-on of stablizer is 0.1~5.0m% of solid materials amount, preferably 0.1~1.0m%.
Described carbon element solid materials comprises petroleum pitch, refinery coke or its mixture, and both can mix by arbitrary proportion; Described petroleum pitch comprises straight run vacuum residuum solvent deoiling pitch, thermal transition residual oil solvent deoiling pitch, thermal transition condensation pitch, and the bituminous softening temperature is more than 100 ℃; Described petroleum coke comprises the coke that various coking process such as delayed coking, fluid coking, flexicoking are produced.
Described dispersion agent is to adopt a kind of BTX aromatics sulfonate and formaldehyde condenses (trade names PF-200, be a kind of efficient cement water reducing agent), it is to be raw material by aromaticity content greater than 50% 165~365 ℃ distillate, directly and strong sulfuric acid response, acid sludge is made by hydrolysis, formaldehyde condensation.The method that concrete preparation process provides by the patent application of application number 96106515.x.The used raw material of this dispersion agent is the intermediate product of the cat-cracker of petroleum refining industry, and raw material is easy to get, and preparation technology is simple, and environmental pollution is little, and production cost is low.
Described stablizer comprises commercially available carboxymethyl cellulose, water glass, polyvinyl alcohol.
Below in conjunction with accompanying drawing technological process of the present invention is described.
Accompanying drawing is technical process of the present invention.As shown in drawings, carbon element solid material I is milled to less than 40 purpose pitch particle II through passing through fan mill 1, and flows to into sizes of steel balls for coarse grinding mills 2, fine grinding ball mill 3, and the aqueous solution III that on request ratio adds dispersion agent in two ball mills carries out wet-milling simultaneously.In ball mill 2, controlling its linear velocity is 1~1.5 meter per second, obtains slurries IV, and its granularity is between 150~250 orders; In ball mill 3, controlling its linear velocity is 1.5~2.0 meter per seconds, obtains slurries V, and its granularity is between 200~250 orders.Slurries IV, V flow into mixing tank 4 thorough mixing, and add stablizer VI simultaneously, promptly make water slurry finished product VII through agitator 5 abundant stirrings.Above-mentioned all processes all is to carry out under room temperature, normal pressure.
Described sizes of steel balls for coarse grinding mills comprises that general ball mill, its linear velocity of rod mill wet-milling equipment are 1~1.5 meter per second.
Described fine grinding ball mill comprises high-efficient wet-type ball mill, vibration mill wet-milling equipment, and linear velocity is 1.5~2.0/ seconds.
Major advantage of the present invention: owing to adopt two sections wet grinding technologies in parallel, avoid sieving dust from flying, contaminate environment is also avoided in the CN85106713A technology mixing the obstruction that causes transport pipe because of dry powder and slurries simultaneously; The slurry fluidity that the dispersion agent that the present invention selects for use makes is good, and viscosity is all below 1Pa.s; In addition, technical process of the present invention is simple, does not need thickening equipment, has therefore reduced process cost, has shortened the slurrying time.The fuel that the carbon element solid water slurry that the present invention makes can be used as Industrial Boiler, Industrial Stoves also can be used for gas making.
Further describe characteristics of the present invention with example below.
Example 1
(ash content is 1.14% to get softening temperature and be 232 ℃ thermal transition condensation pitch 100kg, volatilization is divided into 42.7%), separated into two parts after fan grinds, wherein 50kg pitch particle, add 0.5kg dispersion agent PF-200 and 25.1kg water, controlling its linear velocity is 1.2 meter per seconds; With remaining 50kg pitch particle, add 0.5kg dispersion agent PF-200 and 25.1kg water, controlling its linear velocity is 1.8 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 0.3kg stablizer carboxymethyl cellulose simultaneously, and under agitator fully stirs, make 151.5kg Pitch Water Slurry finished product at last.Slurry density is 66.0%, and dispersion agent and stablizer account for 1.0%, 0.3% (with respect to pitch) respectively, and>200 purpose granularities account for 85.0%, and viscosity is 0.460Pa.s, and calorific value is 25MJ/kg.Slurries stability was greater than 60 days.
Example 2
(ash content is 0.24% to get softening temperature and be 165 ℃ thermal transition condensation pitch 100kg, volatilization is divided into 68.2%), separated into two parts after fan grinds, 40kg pitch particle wherein, add 0.12kg dispersion agent PF-200 and 29.0kg water, controlling its linear velocity is 1.2 meter per seconds, with remaining 60kg pitch particle, add 0.18kg dispersion agent PF-200 and 43.4kg water, controlling its linear velocity is 1.8 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 0.5kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 173.2kg Pitch Water Slurry finished product at last.Slurry density is 58.0%, and dispersion agent and stablizer account for 0.3%, 0.5% (with respect to pitch) respectively, and>200 purpose granularities account for 82.0%, and calorific value is 23.3MJ/kg, and viscosity is 0.780Pa.s.Slurries stability was greater than 30 days.
Example 3
Get oil delay coke 100kg, separated into two parts after fan grinds, wherein the 60kg pitch particle adds 0.6kg dispersion agent PF-200 and 35.2kg water, and controlling its linear velocity is 1.0 meter per seconds; With remaining 40kg pitch particle, add 0.4kg dispersion agent PF-200 and 23.5kg water, controlling its linear velocity is 1.5 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 0.5kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 160.2kg Pitch Water Slurry finished product at last.Slurry density is 63.0%, and dispersion agent and stablizer account for 1.0%, 0.5% (with respect to pitch) respectively, and>200 purpose granularities account for 84.5%, and calorific value is 22.3MJ/kg, and viscosity is 0.436Pa.s.Slurries stability was greater than 40 days.
Example 4
Get oil delay coke 100kg, separated into two parts after fan grinds, wherein the 54.5kg pitch particle adds 0.22kg powder PF-200 and 32.0kg water, and controlling its linear velocity is 1.4 meter per seconds; With remaining 45.5kg pitch particle, add 0.18kg dispersion agent PF-200 and 26.7kg water, controlling its linear velocity is 1.9 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 0.5kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 159.6kg Pitch Water Slurry finished product at last.Slurry density is 63.0%, and dispersion agent and stablizer account for 0.4%, 0.5% (with respect to pitch) respectively, and>200 purpose granularities account for 84.0%, and calorific value is 22.3MJ/kg, and viscosity is 0.721Pa.s.Slurries stability was greater than 45 days.
Example 5
Get the mixture (pitch: coke=1: 1 of oil delay coke and petroleum pitch (softening temperature is 232 ℃),) 100kg, separated into two parts after fan grinds, wherein 44.4kg pitch particle, add 0.44kg dispersion agent PF-200 and 29.6kg water, controlling its linear velocity is 1.5 meter per seconds; With remaining 55.6kg pitch particle, add 0.56kg dispersion agent PF-200 and 37.1kg water, controlling its linear velocity is 2.0 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 0.5kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 168.2kg Pitch Water Slurry finished product at last.Slurry density is 60.0%, and dispersion agent and stablizer account for 1.0%, 0.5% (with respect to pitch) respectively, and>200 purpose granularities account for 83.5%, and viscosity is 0.122Pa.s.Slurries stability was greater than 50 days.
Example 6
Get softening temperature and be 232 ℃ thermal transition condensation pitch 100kg, separated into two parts after fan grinds, wherein the 50kg pitch particle adds 1.5kg dispersion agent PF-200 and 25.1kg water, and controlling its linear velocity is 1.2 meter per seconds; With remaining 50kg pitch particle, add 1.5kg dispersion agent PF-200 and 25.1kg water, controlling its linear velocity is 1.8 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 0.3kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 153.5kg Pitch Water Slurry finished product at last.Slurry density is 66.0%, and dispersion agent and stablizer account for 3.0%, 0.3% (with respect to pitch) respectively, and viscosity is 0.632Pa.s, and slurries stability was greater than 60 days.
Example 7
Get softening temperature and be 232 ℃ thermal transition condensation pitch 100kg, separated into two parts after fan grinds, wherein the 50kg pitch particle adds 2.5kg dispersion agent PF-200 and 25.1kg water, and controlling its linear velocity is 1.2 meter per seconds; With remaining 50kg pitch particle, add 2.5kg dispersion agent PF-200 and 25.1kg water, controlling its linear velocity is 1.8 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 0.3kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 155.5kg Pitch Water Slurry finished product at last.Slurry density is 66.0%, and dispersion agent and stablizer account for 5.0%, 0.3% (with respect to pitch) respectively, and viscosity is 0.851Pa.s, and slurries stability was greater than 60 days.
Example 8
Get softening temperature and be 232 ℃ thermal transition condensation pitch 100kg, separated into two parts after fan grinds, wherein the 50kg pitch particle adds 0.5kg dispersion agent PF-200 and 25.1kg water, and controlling its linear velocity is 1.2 meter per seconds; With remaining 50kg pitch particle, add 0.5kg dispersion agent PF-200 and 25.1kg water, controlling its linear velocity is 1.8 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 1.0kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 152.2kg Pitch Water Slurry finished product at last.Slurry density is 66.0%, and dispersion agent and stablizer account for 1.0%, 1.0% (with respect to pitch) respectively, and viscosity is 0.461Pa.s, and slurries stability was greater than 70 days.
Example 9
Get softening temperature and be 232 ℃ thermal transition condensation pitch 100kg, separated into two parts after fan grinds, wherein the 50kg pitch particle adds 0.5kg dispersion agent PF-200 and 25.1kg water, and controlling its linear velocity is 1.2 meter per seconds; With remaining 50kg pitch particle, add 0.5kg dispersion agent PF-200 and 25.1kg water, controlling its linear velocity is 1.8 meter per seconds.With two kinds of slurries thorough mixing in mixing tank, add 5.0kg stablizer carboxymethyl cellulose simultaneously, and under the abundant stirring of agitator, make 156.2kg Pitch Water Slurry finished product at last.Slurry density is 66.0%, and dispersion agent and stablizer account for 1.0%, 5.0% (with respect to pitch) respectively, and viscosity is 0.462Pas, and slurries stability was greater than 30 days.

Claims (6)

1, a kind of preparation method of water fluid fuel with solid carbon, its characteristics are to adopt two sections wet grinding technologies in parallel, and concrete preparation process is followed successively by:
(1), the carbon element solid materials is ground to less than behind 40 orders, and flow to into rough grinding machine and fine grinder, and in two shredders, add dispersion agent and water simultaneously, rough grinding machine linear velocity is 1~1.5 meter per second, obtain containing 150~250 order particulate slurries, the fine grinder linear velocity is 1.5~2.0 meter per seconds, obtains containing 200~250 order particulate slurries, the add-on of dispersion agent and water is respectively the 0.1~5.0m% and the 43~82m% of solid materials amount
(2), two kinds of slurries that (1) step was obtained mix and add stablizer, can obtain the water slurry product that concentration is following particle>75% of 55~70% and 200 orders through abundant stirring, the ratio of mixture of two kinds of slurries is 2~3: 3~2, and the add-on of stablizer is 0.1~5.0m% of solid materials amount.
2, by the described method of claim 1, it is characterized in that described carbon element solid materials is petroleum pitch, petroleum coke or its mixture.
3, by the described method of claim 2, it is characterized in that described pitch, its softening temperature is more than 100 ℃.
4, by the described method of claim 1, it is characterized in that described dispersion agent is a kind of BTX aromatics sulfonic formaldehyde condensation compound.
5, by the described method of claim 1, it is characterized in that described stablizer comprises carboxymethyl cellulose, water glass, polyvinyl alcohol.
6, by the described method of claim 1, it is characterized in that described stablizer is a carboxymethyl cellulose.
CN97103965A 1997-04-09 1997-04-09 Preparation process of water fluid fuel with solid carbon Expired - Lifetime CN1054394C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007124681A1 (en) * 2006-04-24 2007-11-08 Guangzhou Devotion Thermal Technology Co., Ltd. Desulfurizing coke-water slurry and process for preparation thereof
CN102746912A (en) * 2012-06-18 2012-10-24 北京金骄生物质化工有限公司 Coal-water slurry fuel and preparation method thereof
CN105694940A (en) * 2016-04-25 2016-06-22 秦皇岛华瑞煤焦化工有限公司 Bituminous grout production method
CN106147909A (en) * 2015-04-14 2016-11-23 秦皇岛弘耀节能玻璃有限公司 A kind of preparation method of activity hydrocarbon powder solid fuel composition

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU597531B2 (en) * 1985-07-23 1990-05-31 Fuji Oil Company Limited Process for producing coal-water slurry at high concentration
CN85106713B (en) * 1985-09-06 1986-11-26 中国科学院感光化学研究所 Manufacturing engineering for high concentration water coal

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007124681A1 (en) * 2006-04-24 2007-11-08 Guangzhou Devotion Thermal Technology Co., Ltd. Desulfurizing coke-water slurry and process for preparation thereof
CN102746912A (en) * 2012-06-18 2012-10-24 北京金骄生物质化工有限公司 Coal-water slurry fuel and preparation method thereof
CN106147909A (en) * 2015-04-14 2016-11-23 秦皇岛弘耀节能玻璃有限公司 A kind of preparation method of activity hydrocarbon powder solid fuel composition
CN105694940A (en) * 2016-04-25 2016-06-22 秦皇岛华瑞煤焦化工有限公司 Bituminous grout production method

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