The viscosity reduction by decomposition of naphthenic acids in hydrocarbon oil exposure at elevated temperature

 

(57) Abstract:

The invention relates to reducing the viscosity of hydrocarbon by heating. How are heat treatment of the raw material with an acid number greater than 2 mg KOH 1 g at a temperature in the treatment area of about 204C. for a time sufficient to substantially reduce the viscosity of the raw material with simultaneous removal of gaseous reaction products from the treatment area during a specified heat treatment operations. The method allows to reduce the viscosity of crude oil or its fractions having a high total acid number. 8 C.p. f-crystals, 3 tables.

This invention relates to reducing the viscosity of hydrocarbon oils by heating.

Most crude oils having a high total acid number according to ASTM D-664 (OCC), usually 2 mg KOH/g or more, are also very viscous. This increases the problems associated with the operation of, for example, in the case of oil wells, because of the additional energy costs for pumping crude oil to the ports for shipment. The use of exposure at elevated temperatures near the place of receipt reduces the viscosity, which reduces the cost of maintenance of the pipelines and pajalich crude oil at the place of their reception, because it facilitates the transportation through pipelines where it is the preferred initial method of transportation. Crude oil with a lower viscosity can be transported by pipeline with less cost, because it requires a smaller investment due to the smaller diameter pipes, the smaller the heating of crude oil or its absence and/or lower energy costs for pumping down the line.

This invention is a method of reducing the viscosity of crude oils or of fractions of crude oils having a high total acid number (OCC). This invention involves a heat treatment of raw materials in the treatment zone at a temperature of at least about 204oC (400oF) during a period of time sufficient to effect the reduction of viscosity. Such heat treatment significantly reduces the acid number of the crude oil. It is known that acids can increase the viscosity of crude oils, for example, through hydrogen bonds (Fuel, 1994, 73, 257-268). Under this treatment the acid decomposed and, therefore, can no longer participate in the formation of hydrogen bonds, thereby reducing the viscosity of treatment compared to the original crude oil is of STATCOM after vacuum distillation until the temperature sufficient to reduce the viscosity of the residue (see , for example, Petroleum Refining: Technology and Economics, J. H. Gary and Glenn E. Handwork, 3rd edition. Marcel Dekker, New York, 1994, pp. 89-94). This process (slight cracking) reduces the viscosity of the residue by breaking ties and a significant reduction of the molecular mass of molecules. It also significantly changes other properties of the product such as its stability during storage. In this invention the machining conditions are softer, and therefore the storage stability of the product does not change significantly. This is applicable to crude oils with high acid numbers, because the decomposition of the acid takes place under milder conditions (lower temperatures and/or within a smaller period of time) than severing ties to a significant reduction in molecular weight. In the processing according to this invention may occur a decrease in molecular weight, but the overriding objective is to reduce the viscosity due to the decomposition of acids.

The feedstock, which can be effectively treated with this method of heat treatment includes potenziani crude oil or fractions containing naphthenic acid. Fraction of crude oil that can be processed are of FDS is tanovich acids}, the fuel oil atmospheric distillation of crude oil and vacuum gas oils, for example, when 343-566oC (650-1050oF). The preferred feedstock includes potenziani and stripped of crude oil and vacuum gas oils, particularly preferred potenziani and stripped of crude oil.

This feedstock can be processed at a pressure above atmospheric, atmospheric or below atmospheric, for example, when 9,81 - 9810 kPa (0.1 - 100 ATA), preferably less than 1470 kPa (15 al), more preferably 98,1 - 981 kPa (1 to 10 bars) and preferably in an inert atmosphere, for example in an atmosphere of nitrogen or other gases, non-oxidants. Since the heat treatment leads to the decomposition of the acid, it is necessary to provide suvcw gaseous decomposition products, i.e. water vapor, CO2and CO, as well as products of cracking. Especially it is necessary to continuously remove the water vapor formed by the decomposition of acids or by evaporation of the water contained in the original oil in order to minimize the inhibition of decomposition of the acid. All light fractions or light products of cracking hydrocarbons can be separated by condensation and, if desired, is connected with the processed raw materials. In practice providea performance should also blow CO2and CO. This purge gas can be natural gas or other light hydrocarbon gases, which usually can be available at the refineries or plants. The feed rate of the purge gas should be in the range of 0.07 - 140,8 m3/m3(1 - 2000 standard cubic feet per barrel of feedstock, SCF/BbI).

Since the treatment depends on temperature and time, the temperature should preferably be in the range 316-427oC (600-900oF), more preferably 371-426oC (700-800oF). The processing time (the time when heated) can vary within wide limits and be in inverse proportion to temperature, comprising, for example, from 30 seconds to about 10 hours, preferably between 1 and 90 minutes, more preferably 30 to 90 minutes. Of course, at any given temperature more processing time, will generally result in lower viscosities, but avoid exceeding a specified higher level of cracking.

As already mentioned, for carrying out the process, you can use the reaction chamber both periodic and continuous action. Expert engineers can consider the use of tubular react, however, in no way his limit.

Example 1

The experiments were conducted in an open reactor (all, except as specifically mentioned), including distillation equipment similar to that described in ASTM D-2892 or ASTM D-5236. Approximately 300 grams of sample fractions of crude oil at 343oC+ (650oF+) was placed in a distillation flask. {Whole crude oil is not used, although it is certainly suitable for processing to avoid physical loss of part of the sample at 343oC- (650oF-)}. The sample was rapidly heated to the desired temperature and held at this temperature for up to six hours in an inert atmosphere, for example under nitrogen atmosphere. Mixing was carried out or by bubbling nitrogen through the sample or, preferably, by stirring with a magnetic stirrer. Periodically, taking aliquots for measurement of viscosity.

In a series of experiments was carried out by decomposition of naphthenic acids during thermal treatment, depending on temperature and time.

The process is carried out in an open reactor with nitrogen purging to remove gaseous reaction products, such as hydrocarbons, C1-C4water vapor, CO2and CO. Measured viscosity in Centistokes (cSt) at 40oC (1041.

As can be seen from the table. 1, the decrease of the viscosity follows the decrease in OKC, and the percent reduction increased with increasing temperature and/or time of the heat treatment.

Example 2

In another series of experiments studied the decomposition of naphthenic acids depending on the temperature and rate of purge gas during the heat treatment in an autoclave using potenziani crude oil. In experiment 1 and experiment-2 the resulting gases were constantly blown away by the helium speed is 224.4 m3/m3(1275 SCF/Bbl), and in experiment 3 the resulting gases leaving the reactor, so that the excess pressure was increased up to a maximum 787 kPa (100 psig excess.). Determined viscosity at 40oC (104oF) and OCC; the results are shown in table. 2.

These results confirm that higher processing temperatures, leads to a lower viscosity and OKC potenziani crude oil (compare experiments 1 and 2). The results also show that the blow-off gas from the reaction zone reduces the pressure in the reaction vessel and leads to a lower viscosity and greater reduction OCC (compare experiments 2 and 3).

Example 3

The following series of experiments were conducted to assess the impact of water vapor, CO2and CO to reduce the viscosity at taxidi carbon was present only due to the decomposition of naphthenic acids, was measured the lowest viscosity, corresponding to the most significant reduction in OKC (87,6%). In experiment 2 to blown gas were added only water vapor, and there was obtained a higher viscosity and lower %OCC. When part of the partial pressure of water vapor was replaced by CO2and CO., in experiments 3 and 4 also observed the effect of relatively higher viscosity and a smaller reduction %OCC respectively, which shows the inhibitory effect of water, strengthen CO2or CO.

1. The way to reduce the viscosity of hydrocarbons having a total acid number (OCC) more than 2 mg KOH/g by heat treatment at a temperature in the treatment area at least 204oC for a time sufficient to substantially reduce the viscosity of hydrocarbons with simultaneous removal of gaseous reaction products from the treatment area during a specified heat treatment operations.

2. The method according to p. 2, where in the process are formed gaseous products of the reaction of CO, CO2and water vapor, which is simultaneously removed from the treatment area during the heat treatment operations.

3. The method according to p. 1, where in the process are formed gasiorski during the heat treatment operations.

4. The method according to p. 1, in which the treatment temperature is at least about 316C.

5. The method according to p. 1, in which the treatment temperature is in the range of about 316-482N

6. The method according to p. 1, in which the heat treatment time is in the range from about 1 min to 10 h

7. The method according to p. 1, in which the feedstock is potenciana crude oil.

8. The method according to p. 1, in which the raw material is stripped crude oil.

9. The method according to p. 1, in which the pressure treatment is about 98,1-981 kPa (1-10 atmospheres).

Priority points:

20.10.1995 under item 1;

12.12.1995 on PP.2-9.

 

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