Method for treating petroleum or natural gas

Abstract

A method for treating petroleum, petroleum fraction, or natural gas, the process comprising: adding a) a first component which is selected from material, particularly roots, of a plant of the genus Glycyrrhiza, and/or an arbuscular mycorrhizal fungi, and b) a second component which is selected from a plant material or -ingredient comprising plastids, algae and/or cyanobacteria,
to the petroleum, petroleum fraction, or natural gas.

Claims

1. A method for treating petroleum, a petroleum fraction, or natural gas, comprising: adding a) a first component comprising arbuscular mycorrhizal fungi, and b) a second component comprising a plant material comprising plastids, a plant ingredient comprising plastids, and/or cyanobacteria, to the petroleum, petroleum fraction, or natural gas, wherein the method reduces sulfur and/or sulfur compounds in the petroleum, the petroleum fraction, or the natural gas.

2. The method of claim 1, wherein the first component and second component that are added to the petroleum, or petroleum fraction, which is to be treated, are comprised in a first petroleum, or first petroleum fraction, wherein the first petroleum, or first petroleum fraction is added to the petroleum, or petroleum fraction which is to be treated.

3. The method of claim 1, further comprising: c) adding the petroleum, or the petroleum fraction, that was treated by adding the first component and the second component to a further petroleum, or a further petroleum fraction, that has not yet been treated by the method, and d) optionally repeating step c) once or more, thereby treating a still further petroleum or petroleum fraction, that has not been treated before.

4. The method of claim 1, comprising: adding a liquid hydrocarbon to the petroleum, or the petroleum fraction, after it was treated by adding the first component and the second component.

5. The method of claim 1, further comprising: washing the petroleum, or the petroleum fraction, after it was treated by adding the first component and the second component, with an aqueous liquid phase.

6. The method of claim 1, wherein the plant material or plant ingredient is from a plant of the genus Olea.

7. The method of claim 1, wherein the plant material or plant ingredient is a plant oil or a plant extract.

8. The method of claim 1, wherein the plant material or plant ingredient comprises a phenylethanoid compound.

9. The method of claim 1, wherein the arbuscular mycorrhizal fungi is from the genus Glomus and/or the genus Acaulospora.

10. The method of claim 1, wherein adding the first and the second component comprises: adding the second component to the petroleum, petroleum fraction, or natural gas, allowing the petroleum, petroleum fraction, or natural gas to stand, and adding a mixture of the first and the second component the petroleum, petroleum fraction, or natural gas.

11. The method of claim 1, comprising adding a further component to the petroleum, petroleum fraction, or natural gas, wherein the further component is a biocide, at least one amine, at least one quaternary ammonium compound, or a mixture thereof.

12. The method of claim 1, wherein the method increases API gravity in the petroleum, the petroleum fraction, or the natural gas.

13. The method of claim 1, wherein the method decreases viscosity in the petroleum, the petroleum fraction, or the natural gas.

Description

BRIEF DESCRIPTION OF THE FIGURES

(1) FIG. 1 shows a schematic flow diagram of a process of the invention for the treatment of a subterranean petroleum reservoir;

(2) FIG. 2 shows a schematic flow diagram of a process of the invention for the treatment of petroleum and its fractions in surficial recovery plants and downstream refining and processing facilities;

(3) FIG. 3 shows a schematic flow diagram of a process of the invention for the treatment of a subterranean natural gas reservoir;

(4) FIG. 4 shows a schematic flow diagram of a process of the invention for the treatment of natural gas in downstream refining and processing facilities;

EXAMPLES

Example 1: Preparation of an Addition Agent of the Invention

(5) The following procedure relates to preparation of concentrated chemo-biological fermentation solution, which is also called a “lichen” solution.

(6) 1.1 STEP NO. 1: Preparation of Maceration of “Glycyrrhiza glabra/Licorice” A. Soak 2000 g of licorice in 435 g of suitable aromatic solvent such as Xylenes C.sub.8H.sub.10 (about 500 ml). B. Soaking is encountered in ten steps at every step soak 200 g of licorice with the same volume amount of Xylenes. C. The reaction time is 10-14 hours between every step. Total reaction time=10-14 hours×10=100-140 h.

(7) 1.2 STEP NO. 2: Preparation of a Virgin (Bitter) Olive Oil Solution A. Add 400 ml of bitter olive oil+1000 ml of Xylenes (concentration 28.5%). B. Add 300 ml Pentan-1-ol C.sub.5H.sub.12O. C. Add 500 ml methanol.

(8) 1.3 STEP NO 3: Preparation of Refined Olive Oil Solution A. Add 500 ml of refined olive oil+1000 ml of Xylenes (concentration 33%). B. Add 300 ml Pentan-1-ol C.sub.5H.sub.12O. C. Add 500 ml methanol.

(9) 1.4 STEP NO 4: Preparation of Reverse Demulsifier-De-Oiler (Polyacrylamide Flocculant) Add 500 ml of chemical SpectraFloc™ 875+1000 ml of Xylenes (concentration 33%).

(10) 1.5 STEP NO 5: Preparation of Chalcone Chemical Add 250 g of Chalcone+870 g Xylenes.

(11) 1.6 STEP NO 6: Prepare 1750 ml of Toluene.

(12) 1.7 Preparation of Final Mixture The products of above-mentioned steps are mixed with exposure to light. a) Mix STEP NO 2 product with STEP NO 1 product, encounter the complex mix in reaction time 10-14 h. b) Add STEP NO 3 product to mix, in reaction time 10-14 h c) Add STEP NO 4 product to mix, in reaction time 10-14 h d) Add STEP NO 5 product to mix, in reaction time 10-14 h e) Add STEP NO 6 product to mix, in reaction time 10-14 h, thereby obtaining the addition agent of the invention.

(13) Amounts of chemicals:

(14) 400 ml of Virgin Olive Oil

(15) 500 ml of refined Olive Oil

(16) 600 ml of Pentan-1-ol

(17) 1000 ml of Methanol

(18) 500 ml of SpectraFloc™ 875

(19) 4500 ml of Xylenes

(20) 1750 ml of Toluene

(21) 250 g of Chalcone

(22) 2000 g of Licorice

(23) For following examples see also the list of reference symbols as enclosed.

Example 2: Treatment of a Subterranean Petroleum Reservoir

(24) A specific embodiment of the process is the treatment of a subterranean petroleum reservoir RV (FIG. 1) via downhole injection. The treatment solutions are prepared in the vessels PV110, PV120 and PV130. PV110 mixes cyanobacteria or olive oil (refined and bitter mixture) (CF110) with kerosene (SF110), PV120 mixes biocide (glutaraldehyde, NovaCide 1125™ by Nova Star LP), and amine/quaternary ammonium compound (one or more of corrosion inhibitors Nova Star NS-1435™, NS-1442™, NS-1471™, NS-2129™, NS-1445™ by Nova Star LP) (CF120) with water (SF120) and PV130 mixes the additive produced in example 1, supra (CF130)—with kerosene (SF130). PV130 then feeds the fermentor PV140. The actual treatment is done in two stages: 1. Batch sequential injection with shut-in wellhead. First, the extractor treatment solution from PV120 in concentrations of around 2% and 5% respectively, is pumped into the downhole DH with high pressure pumps where it is injected into the reservoir RV sequentially via injection tubing IT. The reaction interval time is about 12 hours after each injection; this initial cycle consists of four steps and can be repeated as required based on sample laboratory analysis results. Second, the reactor treatment solution from PV110 in concentration of around 20% is pumped into the downhole DH with high pressure pumps where it is injected into the reservoir RV via injection tubing IT. This stage inhibits SRB growth and reduces their bioactivity. H.sub.2S and sulfur are reduced by about 50% at this stage as the sulfur content in crude oil is proportional to the SRB colony population within crude oil. 2. Continuous partial injection with flowing well. A portion of the production crude oil stream (5% to 15%) is forwarded to fermentor vessel PV140 for treatment by adding around 10% of a chemo-biological fermentation solution with ca. 16% concentration. The typical fermentation time in PV140 is about 72 hours. The fermented product from PV140 is pumped into the downhole DH with high pressure pumps where it is injected into the reservoir RV via injection tubing IT continuously to improve the crude oil stream flow through the production tubing PT as required. This stage develops the energetic biological anti-degradation reactions in the reservoir RV formation that enhance the hydrocarbon chains, increase API gravity, decrease viscosity, and reduce sulfur contents and H.sub.2S concentration by about 90%.

(25) The quantity of treatment solutions to be injected and number of cycles is determined specifically for each well as it depends on various factors, e.g. the composition of the crude oil, the production volume and treatments targets. The initial bio-reaction retention time in the reservoir RV is minimum 24 hours.

(26) The embodiment of the invention according to FIG. 1 particularly reduces sulfur, salts and heavy metals content, lowers the H.sub.2S concentration to harmless levels (<10 ppm), increases API gravity and decreases viscosity in the product PR.

Example 3: Treatment of Petroleum or Petroleum Fractions in Surficial Recovery Plants and Downstream Refining and Processing Facilities

(27) Another specific embodiment of the process is the treatment of petroleum and petroleum fractions (FIG. 2) in surficial recovery plants and downstream refining and processing facilities. The treatment solutions are prepared in the vessels PV240, P250 and PV290. PV240 mixes cyanobacteria or olive oil (CF210) with kerosene (SF210), PV250 mixes biocide and amine (products as in example 2 supra) (CF220) with water (SF220) and PV290 mixes the addition agent produced in example 1, supra (CF230)—with kerosene (SF230). PV290 then feeds the fermentor PV260. The actual treatment is done as follows: A feed stock FS portion (ca. 20%) from the production manifold or storage facility is routed into PV210 for separation of gas and water (water is extracted via drain DR) from the crude oil by gravity segregation. The separated crude oil stream is heated in HE210 to ca. 80 Celsius before being forwarded to extractor PV220. The heated crude oil stream in PV220 is injected sequentially with extractor treatment solution (around 20% of the heated crude oil quantity) from PV250 in concentrations of around 2% and 5%, respectively. The reaction interval time is about 12 hours after each injection; this initial cycle consists of four steps and can be repeated as required based on sample laboratory analysis results. The extracted SRB in the bottom water (sludge) of PV220 are removed via the blowdown BD at the end of each reaction cycle. When the reaction is complete, the downstream product is forwarded to reactor PV230. Here it is injected with reactor treatment solution from PV240 (around 5-10% of the intermediate product volume) in concentration of around 20%. The bio-reaction time in reactor PV230 is about 12 hours (without water draining). When the reaction is complete, the downstream product is forwarded to fermentor PV260. Here it is injected with a chemo-biological fermentation solution from PV290 (around 15% of the intermediate product volume) in concentration of around 16%. The typical fermentation time in PV260 is about 72 hours. The fermentation process gain in PV260 in terms of volume of downstream product is in the range of 30% to 50%. When the reaction is complete, the fermented product is forwarded to product mixer PV270 or it may be used directly, e.g., as a high energy, clean fuel for combustion engines or turbines in conjunction with fuel injection system modification accommodating for the higher calorific value of these raffinates RA. In PV270, the fermented product is mixed with the remaining 80% of feedstock FS. The bio-reactivity of the fermented oil in PV270 is highly efficient and dynamic. The energy flow to increase the Gibbs energy of the hydrocarbons (their calorific value) happens on the account of the complete inhibition of SRB, utilizing its stored energy (even from its decomposed dead cells) in the anabolism of the new hydrocarbon chains. The typical reaction time in PV270 is about 72 hours. When the reaction is complete, the finished product is forwarded to PV280, ready for shipment. A portion of the finished product PR from product tank PV280 may serve as makeup for the fermentor PV260 as required. The fermentor PV260 can be composed of one or more physical vessels to shorten cycle times, e.g. one in reaction complete state, one in makeup state and one in fermented product delivery state.

(28) Typical feedstock and treatment parameters are listed in the table below.

(29) TABLE-US-00001 Measurements Bottom Reference Sediment and Point API Gravity Sulfur, % Water, % Salt, PTB Feedstock FS, 24.8 1.89 4 398 untreated Fermenter 33 0.95 0.8 80 Inlet Fermenter 35 0.23 0.5 49 Outlet (Raffinates RA) Finished 44 0.08 nil 7 Product (Product PR)

(30) So called raffinates RA corresponds to an ultralight sweet petroleum quality. Product PR corresponds to a light sweet petroleum quality.

(31) The benefits of the embodiment of FIG. 2 are comparable to FIG. 1, i.e. one or more of above-mentioned benefits can be reached. Moreover, it generates high energy, clean raffinates RA.

(32) The quantity of treatment solutions to be injected and number of cycles is determined specifically for each application as it depends on various factors, e.g. the composition of the crude oil, the production volume and treatments targets.

Example 4: Treatment of Sour Natural Gas in a Subterranean Natural Gas Reservoir

(33) FIG. 3 shows a natural gas reservoir RV. Fermentor Solution mixer PV310 mixes the addition agent produced in example 1, supra (CF310)—with methanol (SF310). The mix is fed into the natural gas reservoir RV via injection tubing IT. Treated (i.e. sweetened) natural gas is obtained as a product PR from the production tubing PT.

Example 5: Treatment of Natural Gas in Downstream Refining and Processing Facilities

(34) In FIG. 4, fermentor solution mixer PV410 mixes the product produced in example 1, supra (CF410)—with methanol (SF410). The mix is fed into the pipeline between feedstock FS and separator PV420 with the liquids (black water and condensate) extracted via drain DR. So, the natural gas from the feedstock FS is treated during flowing through the pipeline. Moreover, the mix from PV410 is also fed into the separator PV420 itself to treat natural gas in the separator. Solutions of biocide and amine treatment can be applied in addition to the above-described procedure.

(35) The embodiments in FIGS. 3 and 4 reduce sulfur (sweeten sour gas), increase the heat rate, decreases the specific gravity and lowers the H.sub.2S concentration to harmless levels (<10 ppm).

(36) It has to be emphasized that above examples illustrate the essence of the invention. The details, such as amounts and concentrations may vary from application to application (e.g. kind of feedstock, treatment target, man-made plant or natural reservoir) without leaving the scope and idea of the invention.

Example 6: Treatment of Oil Sand

(37) Oil sand, as mined, was placed into a vessel.

(38) In the next step, addition agent of the invention, as prepared in example 1, was added to the vessel. The process was accelerated by stirring or tumbling.

(39) After a retention time of 1 h, for which the above mixture is allowed to stand, easy accessible hydrocarbons (>50%) were separated from the non-organic solids and transformed into crude oil-like product.

(40) The obtained crude oil-like product was siphoned off. Hot water (>80° C.) was added in order to accelerate the transformation of the remaining solidified hydrocarbons into crude oil-like product. This transformation needed about 24 h. The process was accelerated by stirring or tumbling.

(41) Remaining non-organic solids were completely stripped of hydrocarbons. After the clean crude oil-like product has been siphoned off, the wash water could be recirculated, possibly after some treatment, if required (e.g. sulfates extraction).

Example 7: Preparation of Addition Agent

(42) 1. Glycyrrhiza, particularly Glycyrrhiza glabra was put into ethanol (alternatively fuel, diesel fuel, and/or pure liquid aromatic hydrocarbon) and allowed to stand for some days. 2. As optional component Saussurea costus was put into ethanol (alternatively fuel, diesel, and/or pure liquid aromatic hydrocarbon) and allowed to stand for some days. 3. Olive oil was added to 1., or both componts from 1. and and 2. were mixed and olive oil added. Further ethanol may be added. 4. After some days Xylene was added, or alternatively (diesel) fuel, methanol, butanol, as “Substrates and Carriers”. The carrier is selected according to the desired use. For example, the addition agent should have a thin viscosity in order to be dispersed into natural gas, if natural gas should be treated.

(43) Above examples were repeated with other sources of plastids or cyanobacteria than the olive oil which was used in above examples. For example, oil from other plants, or plant material from other plants comprising plastids or cyanobacteria also performed well.

Further Examples

(44) Further examples could be performed with any combinations of

(45) a) Glycyrrhiza, and/or arbuscular mycorrhizal fungi (first component), and

(46) b) plastids, algae and/or cyanobacteria (second component)

(47) Specific examples of Glycyrrhiza, arbuscular mycorrhizal fungi and cyanobacteria are mentioned in the detailed description, and these could be used in any combination. Similar procedures as explained above could be employed.

LIST OF REFERENCE SYMBOLS

(48) FIG. 1: IT: Injection Tubing PT: Production Tubing PR: Product DH: Downhole RV: Reservoir PV110: Reactor Solution Mixer PV120: Extractor Solution Mixer PV130: Fermentor Solution Mixer PV140: Fermentor CF110: Reactor Chemicals Feed CF120: Extractor Chemicals Feed CF130: Fermentor Chemicals Feed SF110: Reactor Solvent Feed SF120: Extractor Solvent Feed SF130: Fermentor Solvent Feed

(49) FIG. 2: FS: Feedstock PR: Product DR: Drain BD: Blowdown RA: Raffinates PV210: Separator HE210: Heater PV220: Extractor PV230: Reactor PV240: Reactor Solution Mixer PV250: Extractor Solution Mixer PV260: Fermentor PV270: Product Mixer PV280: Product Tank PV290: Fermentor Solution Mixer CF210: Reactor Chemicals Feed CF220: Extractor Chemicals Feed CF230: Fermentor Chemicals Feed SF210: Reactor Solvent Feed SF220: Extractor Solvent Feed SF230: Fermentor Solvent Feed

(50) FIG. 3: IT: Injection Tubing PT: Production Tubing PR: Product DH: Downhole RV: Reservoir PV310: Fermentor Solution Mixer CF310: Fermentor Chemicals Feed SF310: Fermentor Solvent Feed

(51) FIG. 4: FS: Feedstock PR: Product DR: Drain PV410: Fermentor Solution Mixer PV420: Separator CF410: Fermentor Chemicals Feed SF410: Fermentor Solvent Feed