CN1111583C - Vacuum residuum emulsifying process - Google Patents
Vacuum residuum emulsifying process Download PDFInfo
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- CN1111583C CN1111583C CN 98125094 CN98125094A CN1111583C CN 1111583 C CN1111583 C CN 1111583C CN 98125094 CN98125094 CN 98125094 CN 98125094 A CN98125094 A CN 98125094A CN 1111583 C CN1111583 C CN 1111583C
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- vacuum residuum
- formaldehyde condensation
- residuum
- residual oil
- emulsification method
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Abstract
The present invention relates to a depressurized residuum emulsifying method. In the method, depressurized residuum, water and emulsifying agents comprising petroleum sulfonate methanal condensation compounds are mixed and are uniformly stirred. Because the method adopts cheap and easily obtained petroleum sulfonate formaldehyde condensation compounds as the main components of emulsifying agents, the method reduces the cost of emulsifying agents; compared with sodium polystyrene sulfonate, sulfonic acid sodium salt methanal condensation compounds or sodium lignosulfonate, under the same addition quantity of the petroleum sulfonate formaldehyde condensation compounds, obtained emulsified residuum has low viscosity and stability which can satisfy requirements.
Description
The invention belongs to the oil fuel preparation method of emulsion, exactly is the emulsification method of vacuum residuum.
The burnt matter of vacuum residuum and asphalt content height, the viscosity ratio long residuum is much bigger, surpasses 2000mm sometimes as 100 ℃ of kinematic viscosity
2/ s.Vacuum residuum can be used as catalytically cracked material or boiler oil and uses, but could use after must being heated to 200～300 ℃ or higher temperature, otherwise can go wrong in conveying and atomization process.Therefore, reducing viscosity is to improve the key of vacuum residuum service efficiency.Though the method with lightweight oil dilution visbreaking is simple and easy to do, because the price of thinning oil makes the price of finished product oil fuel raise significantly apparently higher than vacuum residuum.
Oil-fired emulsifying agent and the emulsification method reported are a lot, but be mostly at long residuum and bituminous, for example, the flat 1-313594 of TOHKEMY has proposed the compound emulsifying agent that nonionogenic tenside such as union base phenol polyethenoxy ether and anionic surface tensio-active agents such as sodium polystyrene sulfonate, naphthalenesulfonic acid-formaldehyde condensate and sodium lignosulfonate are formed, and addition is 0.4～0.8 heavy %.It is the compound emulsifying agent that anion surfactants such as the nonionogenic tenside such as dimeracid of 16～20 higher unsaturated fatty acid and sodium lignosulfonate, sodium alkyl benzene sulfonate are formed that the flat 7-76692 of TOHKEMY has proposed by carbon number, and addition is 0.4～0.8 heavy %.Used heavy oil is petroleum pitch (penetration degree 60～80) and Canadian rock asphalt (12.5 ℃ of softening temperatures), watering quantity 23～45 heavy %.Mentioned emulsifier can obviously reduce the viscosity of emulsified bitumen, but fine chemicals prices such as sodium polystyrene sulfonate and naphthalenesulfonic acid-formaldehyde condensate are higher, is applied to cheap vacuum residuum and can causes its cost to increase.Sodium lignosulfonate is the byproduct of paper industry, is subjected to the restriction of natural resources, and the fluctuation of output and price is all bigger.
The objective of the invention is to above-mentioned defective, a kind of method with cheap emulsifying agent emulsification vacuum residuum is provided at prior art.
The emulsification method of vacuum residuum provided by the invention is with vacuum residuum, water and the emulsifier mix that contains the sulfonated petro-leum formaldehyde condensation products, stirs.
Specifically, the emulsification method of vacuum residuum provided by the invention, being that the emulsifying agent that will contain the sulfonated petro-leum formaldehyde condensation products mixes with water and vacuum residuum, making after the mixing, is benchmark with emulsification residual oil gross weight, residual oil concentration is 60～95 heavy %, preferred 70～85 heavy %, the emulsifying agent total concn is 0.05～0.5 heavy %, preferred 0.1～3 heavy %, more preferably 0.2～1 weigh %, stirring gets final product.
The formaldehyde condensation products of ammonium salt, calcium salt, sodium salt or magnesium salts that described sulfonated petro-leum formaldehyde condensation products can be a mahogany acid.The sulfonated petro-leum formaldehyde condensation products can be synthetic by the petroleum cracking distillate, its preparation method is greater than 50% cracking distillate with the concentrated acid sulfonation aromaticity content, obtain BTX aromatics sulfonic acid, use formaldehyde condensation after the hydrolysis again, at last with alkali or basic oxide neutralization.Described cracking distillate is meant that the boiling range that generates by technologies such as steam cracking, catalytic pyrolysis or catalytic cracking is 200～350 ℃ a distillate.Preparation can be with reference to CN1168360A in detail.
Can also contain nonionogenic tenside in the described emulsifying agent, wherein the weight ratio of sulfonated petro-leum formaldehyde condensation products and nonionogenic tenside can be 1: 0～10, preferred 1: 0～6, more preferably 1: 0～4.Described nonionogenic tenside can be an alkylphenol polyoxyethylene, preferred polyoxyethylene nonylphenol ether or isooctylphenol Soxylat A 25-7, more preferably HLB value (hydrophile-lipophile balance value) is 14～19 polyoxyethylene nonylphenol ether or isooctylphenol Soxylat A 25-7.Described nonionogenic tenside has certain stabilization and visbreaking effect.
In the described emulsifying agent, can also add the stablizer that accounts for emulsifying agent gross weight 0.1～1.0 heavy %, for example, carboxymethyl cellulose, acid polyethylene, polyacrylamide, glue or water glass etc.Function of stabilizer is to improve the stability of emulsification vacuum residuum.
Described vacuum residuum can be the various vacuum residuum of cycloalkyl, intermediate base or paraffinic base.
For the ease of operation, described vacuum residuum suitably can be heated in the emulsion process, as be heated to 50～90 ℃, preferred 60～80 ℃, churning time can be 15～60 minutes.
The emulsification method of vacuum residuum provided by the invention also is applicable to long residuum and bituminous emulsification.
The emulsification method of vacuum residuum provided by the invention is owing to selected sulfonated petro-leum formaldehyde condensation products cheap and easy to get main component as emulsifying agent for use, not only reduced the cost of emulsifying agent, and can obviously reduce residual oil viscosity, for example, when residual oil concentration is 74 weight %, add 0.5 heavy % emulsifying agent provided by the invention, vacuum residuum viscosity is reduced to add 1/500～1/50 before the agent.Compare with sodium polystyrene sulfonate, naphthalenesulfonic acid-formaldehyde condensate or this quality sodium sulfonate, adding equally under the dosage, adopt the viscosity of the resulting emulsification residual oil of method of the present invention lower, and stability also can meet the demands.
The invention will be further described below by embodiment.
Emulsification residual oil viscosity uses 4 with NDJ-1 type rotary viscosity design determining in the example
#Rotor is tested under the condition of 60 rev/mins of rotor speeds, and probe temperature is 60 ℃.After the test emulsification vacuum residuum packed in the column type container and under 60 ℃ of constant temperature, to leave standstill.Account for the stability of the per-cent evaluation emulsification vacuum residuum of oil sample total height with the clear water layer height of container bottom after 1,3,7 day, the stability of the more little expression emulsification of this per-cent residual oil is good more.Example 1
Get 100 ℃ of viscosity＞100,000mpa.s Iranian heavy crude vacuum residuum 74 gram, after being heated to 70 ℃, the emulsifier aqueous solution that adds 26 gram dilute with waters, the polyoxyethylene nonylphenol ether (trade name NP30, chemical plant, Lvshun product) that wherein contains 0.2 gram petroleum sodium sulfonate formaldehyde condensation products (trade names PF-200A, compound agent factory of Beijing Huiyuan product) and 0.3 gram HLB=17.4, make emulsification residual oil after stirring 30 minutes under 70 ℃, viscosity and stability see Table 1.Example 2
Getting 100 ℃ of viscosity is＞100,000mpa.s Iranian heavy crude vacuum residuum 60 gram, after being heated to 70 ℃, the emulsifier aqueous solution that adds 40 gram dilute with waters, the polyoxyethylene nonylphenol ether (trade name NP30, chemical plant, Lvshun product) that wherein contains 0.2 gram petroleum sodium sulfonate formaldehyde condensation products (trade names PF-200A, compound agent factory of Beijing Huiyuan product) and 0.6 gram HLB=17.4, make emulsification residual oil after stirring 30 minutes under 50 ℃, viscosity and stability see Table 1.Example 3
Getting 100 ℃ of viscosity is 77,000mpa.s Liaohe River visbreaking residue 85 gram, after being heated to 70 ℃, the emulsifier aqueous solution that adds 15 gram dilute with waters, the polyoxyethylene nonylphenol ether (trade name NP30, chemical plant, Lvshun product) that wherein contains 0.2 gram petroleum sodium sulfonate formaldehyde condensation products (trade names PF-200A, compound agent factory of Beijing Huiyuan product) and 0.3 gram HLB=17.4, make emulsification residual oil after stirring 30 minutes under 70 ℃, viscosity and stability see Table 1.Example 4
Vacuum residuum 95 grams of the Daqing crude oil that to get 100 ℃ of viscosity be 1580mpa.s, after being heated to 70 ℃, add the emulsifier aqueous solution of 5 gram dilute with waters, wherein contain 0.2 gram petroleum sodium sulfonate formaldehyde condensation products, make emulsification residual oil after stirring 30 minutes under 70 ℃, viscosity and stability see Table 1.Example 5
Getting 100 ℃ of viscosity is 13,700mpa.s vacuum residuum 74 gram of Saudi Arabia's light crude, after being heated to 70 ℃, the emulsifier aqueous solution that adds 26 gram dilute with waters, the polyoxyethylene nonylphenol ether (trade name NP10, chemical plant, Lvshun product) that wherein contains 0.2 gram mahogany acid ammonium formaldehyde condensation products (trade names PF-200B, compound agent factory of Beijing Huiyuan product) and 0.3 gram HLB=13.3, make emulsification residual oil after stirring 30 minutes under 70 ℃, viscosity and stability see Table 1.Example 6
Getting 100 ℃ of viscosity is 13,700mpa.s vacuum residuum 74 gram of Saudi Arabia's light crude, after being heated to 70 ℃, the emulsifier aqueous solution that adds 26 gram dilute with waters, the polyoxyethylene nonylphenol ether (trade name NP10, chemical plant, Lvshun product) that wherein contains 0.2 gram petrolic magnesium sulfonate formaldehyde condensation products (trade names PF-200D, compound agent factory of Beijing Huiyuan product) and 0.3 gram HLB=13.3, make emulsification residual oil after stirring 30 minutes under 70 ℃, viscosity and stability see Table 1.Example 7
Getting 100 ℃ of viscosity is＞100,000mpa.s Iranian heavy crude vacuum residuum 74 gram, after being heated to 70 ℃, the emulsifier aqueous solution that adds 26 gram dilute with waters, the isooctylphenol Soxylat A 25-7 (trade name X-100, U.S. combinating carbide company product) that wherein contains 0.1 gram petroleum sodium sulfonate formaldehyde condensation products (trade names PF-200A, compound agent factory of Beijing Huiyuan product) and 0.4 gram HLB=13.5, make emulsification residual oil after stirring 30 minutes under 70 ℃, viscosity and stability see Table 1.Comparative Examples 1
According to the method for example 1, the formaldehyde condensation products of petroleum sodium sulfonate is replaced to sodium polystyrene sulfonate (trade names PSS-4000, compound agent factory of Beijing Huiyuan product), make emulsification residual oil, its viscosity and stability see Table 1.Comparative Examples 2
According to the method for example 1, the formaldehyde condensation products of petroleum sodium sulfonate is replaced to naphthalenesulfonate formaldehyde condensation compound (trade names MT-100, Japanese Kao Co., Ltd. product), make emulsification residual oil, its viscosity and stability see Table 1.Comparative Examples 3
According to the method for example 1, the formaldehyde condensation products of petroleum sodium sulfonate is replaced to sodium lignosulfonate (kahikatea board, village pulp mill product cuts into a mountain), make emulsification residual oil, its viscosity and stability see Table 1.
By contrast as can be seen, the emulsification method of vacuum residuum provided by the invention not only has good visbreaking effect, and resulting emulsification residual oil has satisfactory stability.
Table 1
| Emulsification residual oil | Residual oil concentration, % | Residual oil viscosity before the emulsification, mpa.s | Residual oil viscosity after the emulsification, mpa.s | Stability, % | ||
| 1 day | 3 days | 7 days | ||||
| Example 1 | 74 | ＞100,000 | 150 | 0 | 0 | 0 |
| Example 2 | 60 | ＞100,000 | 180 | 0 | 0 | 0 |
| Example 3 | 85 | 77,000 | 1720 | 0 | 0 | 0 |
| Example 4 | 95 | 1580 | 970 | 0 | 0 | 0 |
| Example 5 | 74 | 13,700 | 605 | 0 | 0 | 0 |
| Example 6 | 74 | 13,700 | 990 | 0 | 0 | 0 |
| Example 7 | 74 | ＞100,000 | 550 | 0 | 0 | 0 |
| Comparative Examples 1 | 74 | With example 1 | 670 | 10 | 13 | 13 |
| Comparative Examples 2 | 74 | With example 1 | 283 | 8 | 8 | 8 |
| Comparative Examples 3 | 74 | With example 1 | 330 | 0 | 0 | 0 |
Claims (8)
1. the emulsification method of a vacuum residuum, it is characterized in that vacuum residuum, water and the emulsifying agent that contains the sulfonated petro-leum formaldehyde condensation products are mixed and stir at 50～90 ℃, after feasible the mixing, with emulsification residual oil gross weight is benchmark, residual oil concentration is 60～95 heavy %, and the emulsifying agent total concn is 0.05～0.5 heavy %.
2. according to the described emulsification method of claim 1, after it is characterized in that mixing, residual oil concentration is 70～85 heavy %.
3. according to the described emulsification method of claim 1, the concentration of emulsifying agent is 0.1～3 heavy % after it is characterized in that mixing.
4. according to the described emulsification method of claim 1, it is characterized in that to contain nonionogenic tenside in the emulsifying agent.
5. according to the described emulsification method of claim 4, the weight ratio that it is characterized in that sulfonated petro-leum formaldehyde condensation products and nonionogenic tenside is 1: 0～10.
6. according to the described emulsification method of claim 5, the weight ratio that it is characterized in that sulfonated petro-leum formaldehyde condensation products and nonionogenic tenside is 1: 0～6.
7. according to the described emulsification method of claim 4, it is characterized in that nonionogenic tenside is an alkylphenol polyoxyethylene.
8. according to the described emulsification method of claim 7, it is characterized in that nonionogenic tenside is selected from polyoxyethylene nonylphenol ether or isooctylphenol Soxylat A 25-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98125094 CN1111583C (en) | 1998-12-04 | 1998-12-04 | Vacuum residuum emulsifying process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98125094 CN1111583C (en) | 1998-12-04 | 1998-12-04 | Vacuum residuum emulsifying process |
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| CN1256301A CN1256301A (en) | 2000-06-14 |
| CN1111583C true CN1111583C (en) | 2003-06-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 98125094 Expired - Lifetime CN1111583C (en) | 1998-12-04 | 1998-12-04 | Vacuum residuum emulsifying process |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104250382B (en) * | 2013-06-28 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of method utilizing nitrobenzene waste water to prepare Emulsion Resid |
| CN105085936B (en) * | 2014-04-25 | 2018-11-02 | 中国石油化工股份有限公司 | A method of preparing Emulsion Resid using PVA device waste water |
| CN104531243A (en) * | 2014-12-30 | 2015-04-22 | 江苏健神生物农化有限公司 | Emulsified slurry oil and preparing method thereof |
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- 1998-12-04 CN CN 98125094 patent/CN1111583C/en not_active Expired - Lifetime
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