WO2014059918A1

WO2014059918A1 - Methanol gasoline core mother liquor and methanol gasoline

Info

Publication number: WO2014059918A1
Application number: PCT/CN2013/085247
Authority: WO
Inventors: 陈茂高; 李裕生; 严锦明
Original assignee: 中懋华能源投资有限公司
Priority date: 2012-10-15
Filing date: 2013-10-15
Publication date: 2014-04-24
Also published as: CN102911743B; CN102911743A

Abstract

The present invention relates to a methanol gasoline core mother liquor and a methanol gasoline prepared using the mother liquor. The compositions thereof in percentage by mass are: solution A: 20-30% of n-octane, 15-25% of n-heptane, 25-35% of methyl tert-butyl ether, and 20-30% of isobutanol; solution B: 20-30% of anhydrous ethanol, 20-26% of hexamethylenetetramine, 5-9% of ammonium nitrate, 15-25% of nitrocellulose lacquer thinner, 12-18% of glycol ether, and 8-12% of dimethylbenzene; solution C: 20-30% of nitroethane, 23-33% of methylcyclohexane, 8-12% of decahydronaphthalene, 13-16% of methylnaphthalene, and 17-27% of phenylmethanol; solution D: 15-25% of nitromethane, 21-31% of n-heptanol, 15-21% of benzotrifluoride, 20-30% of n-octanol, and 9-13% of tetrahydronaphthalene; solution E: 13-53% of isopropanol, 8-12% of metal deactivator T122, 9-14% of corrosion inhibitor T702, 13-17% of cleaning agent T106, and 13-17% of cleaning agent T102; solution F: 50-60% of n-butanol, 20-30% of corrosion inhibitor T747, and 15-25% of corrosion inhibitor T706; and solution G: 40-50% of dimethyl-2-butanone, 13-17% of antioxidant adhesion-proof agent T502, 4-6% of isovaleraldehyde, 12-17% of morpholine, and 15-25% of isopropylbenzene. The methanol gasoline either matches with or surpasses conventional gasoline in terms of energy saving, emission reduction, increased heat value, and increased fuel economy.

Description

Methanol gasoline core mother liquor and methanol gasoline

Technical field

The invention relates to a methanol gasoline core mother liquor and methanol gasoline prepared by using the mother liquor. Background technique

According to the BP World Energy Statistical Yearbook, as of the end of 2011, the global oil reserves were about 1.653 trillion barrels. According to the current globally very conservative consumption rate of 0.8 billion barrels per day, the current world oil reserves are available. Global consumption for 54 years.

As a limited resource, oil will become more and more tense in the face of the development of world industrialization and the heavy use of automobiles. The price of oil has risen from 10.58 US dollars at the end of the last century to 100 US dollars now. The rate of increase is fast in the history of oil. Rarely, it is rare in other large resource products. The soaring oil prices are forcing countries around the world to find alternative energy sources.

China's oil reserves only account for 3% of the world, and oil consumption has soared, household cars have increased, and economic costs have increased. Therefore, China's energy experts agree that energy security strategies must be implemented and every effort must be made to develop oil substitute fuels. In the past two decades, China has accelerated the implementation of its energy strategy and vigorously sought and developed alternative fuels for petroleum.

China is a country that is poor in oil, low in gas and rich in coal. Starting from China's national conditions, finding alternative clean energy from coal-based energy is an important way to solve energy security and sustainable development. On the other hand, with the rapid development of the automobile industry, the rapid increase of urban and rural vehicles has been brought about, and the large use of automobile fuel gasoline has caused serious pollution to the atmospheric environment and seriously threatened the living environment of human beings. Therefore, high-volume, large-scale replacement of automotive cleaning fuels has emerged to address the current over-reliance on oil and the increasing environmental concerns. Among them, the most widely used and fastest growing is methanol gasoline. Due to the wide range of methanol sources, clean fuels and low environmental pollution, it is widely concerned by the automotive industry. Therefore, it is imperative to develop methanol to replace automobile fuel.

China has accumulated sufficient technical basis for designing, manufacturing and operating large-scale methanol plants: Large-scale gasification furnaces with coal-water slurry as raw materials have been in operation for many years, enabling long-cycle operation; new coal-water slurry gasifiers and dry coal pressurization Gasifiers are being actively developed; various low-energy natural gas steam reforming technologies have been mastered; low-cost natural gas conversion to syngas technology using air as a gasifying agent has been developed; various decarbonization and desulfurization processes have been matured. Industrial students Production; conversion, fine desulfurization, methanol synthesis catalysts have been domestically produced; new methanol synthesis reactor has formed a patented technology; distillation equipment has reached energy saving and optimization level. At present, China has mastered the design technology of building a 100,000-300,000 t / a single series methanol plant. Therefore, the use of coal or natural gas to produce methanol, rich sources of raw materials, mature production technology, reasonable price of methanol; methanol gasoline is a high-energy devaluation fuel. At normal temperature, methanol is a liquid, and its storage, transportation, and use are as convenient as gasoline and diesel. The addition of methanol can significantly reduce the emission of harmful substances and is a clean vehicle fuel. Methanol gasoline burns less than harmful substances in the exhaust of the No. 90 gasoline, and has less impact on environmental pollution. The US "DOC" Research Center used 10%-10% gasoline containing methanol to test the results of 10 kinds of cars. When using methanol gasoline on a general gasoline engine, the carbon monoxide in the combustion exhaust gas is reduced by about 30% compared with gasoline, the nitrogen oxides are reduced by 30%-50% compared with gasoline, and the unburned hydrocarbons are reduced by 30%-60%. . The development of methanol gasoline is conducive to the environmental protection of the city. Methanol is the most promising clean fuel in the 21st century. Summary of the invention

SUMMARY OF THE INVENTION The object of the present invention is to provide a high-efficiency low-carbon methanol gasoline core mother liquor which is mixed with methanol and can replace gasoline, so that the automobile can normally travel without changing the structure.

The technical solution of the present invention is as follows:

A methanol gasoline core mother liquor composed of the following liquid compositions expressed by mass percentage content: Liquid A:

Zhengxin 20-30%, Zhenggeng 15-25%, methyl tert-butyl ether 25-35%, isobutanol 20-30%. B liquid:

Anhydrous ethanol 20-30%, hexamethylenetetramine 20-26%, ammonium nitrate 5-9%, nitro diluent 15-25%, ethylene glycol ether 12-18%, xylene 8-12% .

Liquid C:

Nitroacetamide 20-30%, methylcyclohexanyl 23-33%, decalin 8-12%, methylnaphthalene 13-16%, benzyl alcohol 17-27%.

D liquid:

Nitroguanidine 15-25%, n-heptanol 21-31%, trifluorotoluene 15-21%, n-octanol 20-30%, tetrahydronaphthalene 9-13%.

E liquid: Isopropyl alcohol 13-53%, metal passivator T122 8-12%, rust inhibitor T702 9-14%, detergent T106 13-17%, detergent T102 13-17%.

F liquid:

N-butanol 50-60%, rust inhibitor T747 20-30%, rust inhibitor T706 15-25%.

G liquid:

Dimethyl butanone 40-50%, anti-oxidation and anti-adhesive agent T502 13-17%, isovaleraldehyde 4-6%, morpholine 12-17%, isopropylbenzene 15-25%. Each liquid is prepared according to the composition of each of the above liquid compositions A, B, C, D, E, F, G, and then stirred at normal temperature and pressure for 20-40 minutes, respectively, and the liquid composition is equal to ±5%. Mix together, or mix and concentrate for 20-40 minutes in a ratio of ±5% of each liquid composition, that is, a methanol gasoline core mother liquor.

Preferably, the mass percentage of each liquid composition is as follows:

Liquid A:

Zhengxin 25%, Zhengeng 20%, methyl tert-butyl ether 30%, isobutanol 25%.

B liquid:

Anhydrous ethanol 25%, hexamethylenetetramine 23%, ammonium nitrate 7%, nitro diluent 20%, ethylene glycol diethyl ether 15%, xylene 10%.

Liquid C:

Nitroacetam 25%, methylcyclohexane 28%, decalin 10%, methylnaphthalene 15%, benzyl alcohol 22%. D liquid:

Nitroguanidine 20%, n-heptanol 26%, trifluorotoluene 18%, n-octanol 25%, tetrahydronaphthalene 11%.

E liquid:

Isopropanol 48%, metal passivator T122 10%, rust inhibitor T702 12%, detergent T106 15%, detergent T102 15%.

F liquid:

N-butanol 55%, rust inhibitor T747 25%, rust inhibitor Τ 706 20%.

G liquid:

Dimethyl butanone 45%, antioxidant anti-adhesive agent Τ 502 15%, isovaleraldehyde 5%, morpholine 15%, cumene 20%. The present invention provides a methanol gasoline which is prepared by the following method: (1) mixing the above-mentioned methanol gasoline core mother liquor 4-8% with methanol 92-96%, stirring uniformly, and reacting for 20-40 minutes to obtain a denatured alcohol;

(2) mixing the denatured alcohol with a ratio of 75-95% with national standard gasoline or component oil or naphtha 5-25%, and reacting for 20-40 minutes to obtain the methanol gasoline;

The methanol is a refined alcohol having a content of 99.5 to 99.9% or more.

Preferably, the denatured alcohol is mixed with 25% of the national standard gasoline or component oil or naphtha in a ratio of 75%; preferably, the denatured alcohol is in a proportion of 85% with the national standard gasoline or component oil or stone. The brain oil is 15% mixed; preferably, the denatured alcohol is mixed with 5% of the national standard gasoline or component oil or naphtha in a ratio of 95%; preferably, the national standard gasoline is 90#, 93# national standard gasoline . The core mother liquor of the present invention and the methanol gasoline prepared using the core mother liquor have the following characteristics:

1. Unique function to speed up burning. Methanol is different from gasoline. The flash point of gasoline is very low (negative 46 degrees). Its burning speed is very fast. Methanol is higher than gasoline flash point (12 degrees). Its burning speed is slower than that of gasoline. It is not suitable for the combustion characteristics of gasoline engines. Burning or blending methanol has certain difficulties. Since most of the cars are currently set with the combustion characteristics of conventional gasoline, the methanol gasoline prepared by using the high-efficiency low-carbon methanol gasoline core mother liquid of the present invention is normally used for automobiles, and is solved. The problem of methanol effectively replacing gasoline.

2, unique temperature resistance. It can adapt to the large temperature difference and can be used normally under the low temperature of minus 40 degrees and the high temperature of 46 degrees. It fundamentally solves the phenomenon of low temperature non-separation, low temperature easy start, high temperature and no gas resistance. Adaptability of the north and south climate.

3, unique water resistance. It not only resists the moisture absorbed in the air, but also resists the water accumulated in the bottom of the cylinder in the tank. It can also be absorbed by a small amount of water from the outside. It will not separate the oil, emulsification and deterioration, and maximum resistance. The amount of water (adsorption capacity) is between 1.5% and 2%. This water can be absorbed without stirring or cycling.

4, unique ride, good acceleration performance, strong power. The high-efficiency low-carbon methanol gasoline prepared by the core mother liquid of the invention has a Xinxin value of more than 100, has good antiknocking property, sufficient combustion, complete exhaustion, and at the same time improves the heat value of the fuel during combustion.

5. High-efficiency low-carbon methanol gasoline blended with the core mother liquor of the present invention without any modification of any part of the engine. There is no need to add additional fueling equipment to the gas station. The vehicle can be mixed and filled without any modification. It can be used with the national standard gasoline and ethanol gasoline. It can be used alone or interchangeably. 6. High-efficiency low-carbon methanol gasoline blended with the core mother liquor of the present invention has a lower noise than vehicles using national standard gasoline, and various emissions are much lower than those of national standard gasoline vehicles.

The core mother liquor of the present invention is characterized by its high efficiency, low carbon methanol gasoline with good adaptability, smoothness, power, economy, environmental protection and safety. The utility model has the advantages of long storage period, simple production process, normal temperature and pressure, and convenient operation. The high-efficiency low-carbon methanol gasoline, which is prepared by reacting the core mother liquor with methanol, can be adapted to any automobile. detailed description

The following examples illustrate specific embodiments of the invention.

Example:

(1) First, each liquid composition of the mother liquor of the methanol core agent is prepared, and the mass percentage content of each liquid is as follows:

Zhengxin 25%, Zhengeng 20%, methyl tert-butyl ether 30%, isobutanol 25%.

B liquid:

Liquid C:

E liquid:

F liquid:

N-butanol 55%, rust inhibitor T747 25%, rust inhibitor Τ 706 20%.

G liquid:

Dimethyl butanone 45%, antioxidant anti-adhesive agent Τ 502 15%, isovaleraldehyde 5%, morpholine 15%, cumene 20%. Various additives in the invention - metal passivators, rust inhibitors, detergents, anti-oxidation and anti-adhesive agents are commercially available, such as Wuxi Southern Petroleum Additive Co., Ltd., Shenzhen Hongqingtai Petroleum Additive Co., Ltd., Jinzhou Emerging oil The additive liability company produces the product. In this embodiment, the product of Shenzhen Hongqingtai Petroleum Additive Co., Ltd. is selected.

According to the composition of each of the above A, B, C, D, E, F, G liquids, each liquid is prepared, and then stirred at normal temperature and pressure for 30 minutes, and then the liquids are mixed in equal proportions to obtain a methanol gasoline core mother liquor. .

This example employs the liquid compositions in equal proportions, i.e., the proportion of each liquid composition in the methanol vapor core mother liquor is 14.29%. This ratio can fluctuate between 14.29% ± 5%, which is between 9.29-19.29%.

(2) Mixing 4% of the methanol gasoline core mother liquor with 96% methanol, stirring uniformly, and reacting for 30 minutes to obtain denatured alcohol;

(3) mixing the denatured alcohol with 25%, 155%, and 95% of 93# standard gasoline, respectively, and mixing for 30 minutes to obtain the methanol gasoline, respectively. For M75, M85, M95;

The methanol is a refined alcohol having a content of 99.5 to 99.9% or more. The above indicators of methanol gasoline are tested by Shenzhen Institute of Metrology and Quality Inspection, and the results are as follows: Inspection basis Refer to DB 33/T 756.3-2009 "Methanol gasoline for vehicles Part 3: M50",

Reference SH/T0663-1998 "Determination of certain alcohols and ethers in gasoline (gas chromatography)" Test environment (25~30) °C, (50-70) %RH Specification: M75

Single item test item Standard requirement (No. 97)

s

Study fascination value (RON) not less than 97 > 100.0 in accordance with benzene content, % (volume fraction) is not greater than 1.4 0.2, mouth, aromatic content, % (volume

Not more than 22 9.1

Olefin content, % (volume

No more than 19 4.0 payouts) Distillation range:

10% evaporation temperature, °c not higher than 70 57.0

50% evaporation temperature, °C is not higher than 120 64.0 IT port

90% evaporation temperature, °C not higher than 190 66.0

Final boiling point, V is not higher than 205 178.0

Residual amount, % (volume fraction) is not more than 2 0.8

Induction period, min is not less than 480 〉 480 IT port Saturation and vapor pressure, kPa

From May 1 to October 31, no more than 72 56.5 IT port 曰

Water-soluble acid or alkali without IT n actual gum, mg/100mL no more than 5 1.5 IT n unwashed gum, mg/100mL no more than 70 2.5 IT n sulfur content, % (mass fraction) not more than 0.03 0.0004 IT n Lead content, g/L is not more than 0.003 <0.002 IT n iron content, g/L is not more than 0.010 <0.002 IT n manganese content, g/L is not more than 0.018 <0.002 IT n moisture, % (mass fraction) is not more than 0.15 0.06 IT n

Clear and transparent at room temperature, clear and transparent at room temperature, stratified appearance, no suspended matter and no delamination, no suspension IT n

Sediment and sediment

Mechanical impurities None None IT n Low temperature anti-phase separation performance Clear and transparent, no phase separation

Clear and transparent, no phase separation IT n ( -20 V , 4h)

Resistance to phase separation in water, clear and transparent, no phase separation

Clear and transparent, no phase separation IT n (add water 0.15%, 4h)

Copper corrosion (50 ° C, 3 h),

Not more than 1 La IT n level

Methanol content, % (mass score 75.36 Number) Specification Model M85

Single item test item Standard requirement (No. 97)

On the study of the 垸垸 value (RON) not less than 97 > 100.0 in line with benzene content, % (volume fraction) is not greater than 1.4 0.1, the mouth of aromatics content, % (volume

Not more than 22 5.6 pays the number)

Olefin content, % (volume

Not more than 19 2.3 pays the number)

Distillation range:

10% evaporation temperature, °C not higher than 70 60.0

50% evaporation temperature, °C is not higher than 120 64.0

90% evaporation temperature, °C not higher than 190 65.0

Final boiling point, V is not higher than 205 175.0

Residual amount, % (volume fraction) is not more than 2 0.7

Induction period, min is not less than 480 〉 480 pays mouth and mouth steam pressure, kPa

From May 1st to October 31, no more than 72 45.5

Water-soluble acid or alkali without actual solvent, mg/100mL is not more than 5 2.0, unwashed gum, mg/100mL is not more than 70 3.5, sulfur content, % (mass fraction) is not more than 0.03 0.0004 Lead content, g/L is not more than 0.003 <0.002 iron content, g/L is not more than 0.010 <0.002 manganese content, g/L is not more than 0.018 <0.002, mouth water, % (mass fraction) is not more than 0.15 0.06 Pay Clear and transparent at room temperature, clear and transparent at room temperature, layered appearance, no suspended matter and no delamination, no suspended IT deposits and precipitates

Mechanical impurities None None IT port Low temperature anti-phase separation performance Clear and transparent, no phase separation

Clear and transparent, no phase separation

( -20V , 4h ) away

Clear and transparent, no phase separation IT η (add water 0.15%, 4h)

Copper corrosion (50 ° C, 3 h),

Not more than 1 La IT η level

Methanol content, % (mass point

85.62

Number) Specification Model M95

Single item test item Standard requirement (No. 97)

On the study of the singular value (RON) not less than 97 > 100.0 in accordance with the benzene content, % (volume fraction) is not greater than 1.4 <0.1 mouthful of aromatics content, % (volume

Not more than 22 1.7 pays the number)

Olefin content, % (volume

Not more than 19 0.8 pays the number)

Distillation range:

10% evaporation temperature, °C not higher than 70 63.0

50% evaporation temperature, °C not higher than 120 64.0 pay 90% evaporation temperature, °C not higher than 190 64.5

Final boiling point, V is not higher than 205 67.5

Residual amount, % (volume fraction) is not more than 2 0.7

Induction period, min is not less than 480 〉 480 Full and steam pressure, kPa

From May 1 to October 31, no more than 72 33.5 IT port 曰

Water-soluble acid or alkali None No IT port Actual gum, mg/100mL Not more than 5 1.0 IT mouth Unwashed gum, mg/100mL Not more than 70 3.0 IT n

Sulfur content, % (mass fraction) is not more than 0.003 <0.00005 IT n

Lead content, g/L is not more than 0.003 <0.002 IT n

Iron content, g/L is not more than 0.010 <0.002 IT n

Manganese content, g/L is not more than 0.018 <0.002 IT n

Moisture, % (mass fraction) is not more than 0.15 0.07 IT n

Clear and transparent at room temperature, clear and transparent at room temperature,

Appearance Layered, no suspended matter and no delamination, no suspension IT n

Sediment and sediment

Mechanical impurities no no IT n

Low temperature anti-phase separation performance Clear and transparent, no phase separation

Clear and transparent, no phase separation IT n

( -20 V , 4h) away

Clear and transparent, no phase separation IT n

(add water 0.15%, 4h)

Copper corrosion (50 ° C, 3 h),

Not more than 1 La IT n

Level

Methanol content, % (mass point

95.38

In addition, the methanol gasoline of the above embodiment is used for replacing gasoline, and is added to a car. After thousands of people test drive experience, it is reflected that the driving feeling is the same as the use of gasoline.

The results show that the high-efficiency low-carbon methanol gasoline core mother liquor provided by the present invention is mixed with methanol and gasoline, reacts under normal temperature and pressure, and adjusts and changes the properties of methanol gasoline to make its combustion speed and gasification in the engine. Latent heat, explosion resistance, acceleration and resistance to water, frost, corrosion, swelling, gas and cold, hot car start, etc. The performance of the surface meets or exceeds the national standard gasoline, and solves the technical problems of corrosion, swelling, power loss, oil consumption increase, moisture delamination deterioration, low temperature start-up, high temperature gas resistance and the like in the traditional high proportion methanol blending. Reducing consumption, reducing emissions, increasing calorific value, and improving fuel economy are all at or better than traditional gasoline.

Claims

Claim

A methanol gasoline core mother liquor characterized by: each liquid composition represented by a mass percentage content:

Liquid A:

Zheng Xinyu 20-30%, Zheng Geng垸 15-25%, methyl tert-butyl ether 25-35%, isobutanol 20-30%;

B liquid:

Anhydrous ethanol 20-30%, hexamethylenetetramine 20-26%, ammonium nitrate 5-9%, nitro diluent 15-25%, ethylene glycol ether 12-18%, xylene 8-12% ;

Liquid C:

Nitroacetam 20-30%, methylcyclohexane 23-33%, decalin 8-12%, methylnaphthalene 13-16%, benzyl alcohol 17-27%; D solution:

Nitroguanidine 15-25%, n-heptanol 21-31%, trifluorotoluene 15-21%, n-octanol 20-30%, tetrahydronaphthalene 9-13%; E liquid:

Isopropyl alcohol 13-53%, metal passivator T122 8-12%, rust inhibitor T702 9-14%, detergent T106 13-17%, detergent T102 13-17%;

F liquid:

N-butanol 50-60%, rust inhibitor T747 20-30%, rust inhibitor T706 15-25%;

G liquid:

Dimethyl butanone 40-50%, anti-oxidation anti-adhesive agent T502 13-17%, isovaleraldehyde 4-6%, morpholine 12-17%, cumene 15-25%;

The liquid compositions are respectively prepared according to the compositions of the liquid compositions A, B, C, D, E, F, and G, respectively, and then stirred at normal temperature and pressure for 20-40 minutes, respectively, and then the mass ratio of each liquid composition is equal. ± 5% mixed together, or concentrated and stirred for 20-40 minutes in a mass ratio of ± 5% of each liquid composition, that is, a methanol gasoline core mother liquor.

2. The methanol gasoline core mother liquor according to claim 1, wherein the mass percentage of each liquid composition is as follows -

Liquid A: Is 25%, 正 20%, methyl tert-butyl ether 30%, isobutanol 25%;

B liquid:

Anhydrous ethanol 25%, hexamethylenetetramine 23%, ammonium nitrate 7%, nitro diluent 20%, ethylene glycol ether 15%, xylene 10%;

Liquid C:

Nitroacetamide 25%, methylcyclohexane 28%, decalin 10%, methylnaphthalene 15%, benzyl alcohol 22%;

D liquid:

Nitromethine 20%, n-heptanol 26%, trifluorotoluene 18%, n-octanol 25%, tetrahydronaphthalene 11%;

E liquid:

Isopropanol 48%, metal passivator T122 10%, rust inhibitor T702 12%, detergent T106 15%, detergent T102 15%;

F liquid:

N-butanol 55%, rust inhibitor Τ747 25%, rust inhibitor Τ706 20%;

G liquid:

Dimethyl butanone 45%, anti-oxidant anti-adhesive agent Τ 502 15%, isovaleraldehyde 5%, morpholine 15%, cumene 20%.

3. A methanol gasoline characterized by being prepared by the following method:

(1) Mixing 4-8% of the methanol gasoline core mother liquor according to claim 1 or 2 with methanol 92-96%, stirring uniformly, and reacting for 20-40 minutes to obtain a denatured alcohol;

(2) mixing the denatured alcohol with a mass ratio of 75-95% with a national standard gasoline or a component oil or a naphtha 5-25%, and reacting for 20-40 minutes to obtain the methanol gasoline;

The methanol is a refined alcohol having a content of 99.9% or more.

4. The methanol gasoline according to claim 3, wherein:

The denatured alcohol is mixed with 25% of the national standard gasoline or component oil or naphtha in a mass ratio of 75%.

5. The methanol gasoline according to claim 3, wherein:

The denatured alcohol is mixed with 15% by mass of the national standard gasoline or component oil or naphtha.

6. The methanol gasoline according to claim 3, wherein:

The denatured alcohol is mixed with 5% of the national standard gasoline or component oil or naphtha in a mass ratio of 95%.