CN104122321A - Method for measuring acid compounds in petroleum - Google Patents
Method for measuring acid compounds in petroleum Download PDFInfo
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- CN104122321A CN104122321A CN201310155845.3A CN201310155845A CN104122321A CN 104122321 A CN104122321 A CN 104122321A CN 201310155845 A CN201310155845 A CN 201310155845A CN 104122321 A CN104122321 A CN 104122321A
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- 238000000034 method Methods 0.000 title claims abstract description 99
- 239000002253 acid Substances 0.000 title claims abstract description 53
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- 238000000691 measurement method Methods 0.000 abstract 3
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- 238000002239 electrospray ionisation Fourier transform ion cyclotron resonance mass spectrometry Methods 0.000 description 11
- 238000001819 mass spectrum Methods 0.000 description 9
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 8
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 8
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- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 8
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
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- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 229940005605 valeric acid Drugs 0.000 description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
Abstract
The invention relates to a method for measuring acid compounds in petroleum. The method is used for measuring organic acids in a petroleum sample, wherein the molecular weight of the organic acids is less than 180 Daltons. Based on the measurement method, a material used on the surface contacted with petroleum in the crude oil processing process can be determined. Based on the measurement method, a corrosion inhibitor injected into the petroleum processing process can be determined, and the petroleum sample used in the organic acid measurement process comes from the petroleum processing process. Based on the measurement method, the corrosion degree in a petroleum processing system can be monitored, wherein the petroleum sample for measurement and analysis is selected from the petroleum processing system.
Description
Technical field
The mensuration and the application petroleum composition information that the present invention relates to acid compound in oil and Related product are optimized oil refining process.
Background technology
Oil contains complicated hydrocarbon mixture, generally also comprises a small amount of organic acid, as naphthenic acid and phenols.These petroleum acidss can bring the corrosion and scaling such as treating apparatus to petroleum refining process, and the multiple operational issue such as oil-water emulsion.[referring to document: Slavchev et al., British Corrosion J., 1991,34,125-131].Petroleum acids (as naphthenic acid) corrosion is the main etching problem of refinery corrosion, the corrosion of locating as well heater, distillation column and pipeline etc.
Petroleum industry utilizes total acid number (TAN) to describe the corrosive nature of crude oil.According to ASTMD664, the potassium hydroxide milligram number that the whole acidic components during TAN is defined as and in 1 gram of crude oil consume.TAN is higher, the corrosivity of crude oil stronger [referring to document: Qu et al., Corrosion science, 2006,48,1960-1985].Yet the crude oil high with TAN is compared, also there is the relatively low crude oil of some total acid numbers but to there is very strong corrosivity [referring to document: Laredo et al., Energy & Fuels, 2004,18,1687-1694].The corrosivity of crude oil and TAN nonlinear dependence are [referring to document: Smith et al., Energy & Fuels, 2008,23,314-319], corrosivity depends on that the molecular dimension of naphthenic acid in crude oil and/or other acid compound and structure are [referring to document: Hsu et al., Energy & Fuels, 2000,14,217-223].
Based on chemical knowledge, the acid compound in oil has instability when being heated, and when about 200 ° of C, can decompose.From judgement intuitively, the etching problem that total acid number causes should be by crude oil is carried out to heat treated solution, yet really not so in actual production.For example, when high-acid crude oil is in atmospheric distillation operation during with 350 ° of C distillations, there is etching problem [referring to document: Qian et al., Energy & Fuels, 2001,15,1505-1511] in fractionator side line.In other words, if petroleum acids is decomposed into carbon dioxide and hydro carbons like that according to what instruct in prior art, will not there is not etching problem in crude oil so after distillation heating furnace.Inconsistent in theory and practice of total acid number and corrosion problems, impels and does the essence that further research goes to be familiar with better petroleum acids and corrosion reaction mechanism thereof.
Summary of the invention
On the one hand, the present invention proposes the concept that in oil, organic acid is measured, and organic acid molecular mass described herein is less than 180 dalton (Da).
On the other hand, the present invention is based on organic acid in oil and measure process, propose concept definite and oil surface in contact material therefor, and use it in Crude Oil Processing.
On the other hand, based on organic acid in oil, measure process, propose to inject the concept of corrosion inhibiter in petroleum refining process, the oil sample that this organic acid mensuration process is used comes from the petroleum products through processing in this petroleum refining process.
On the other hand, based on organic acid in oil, measure process, propose a kind of concept of monitoring extent of corrosion in petroleum refining system, for the oil sample of determination and analysis, take from this petroleum refining system.
Therefore, the present invention includes following aspect:
In one aspect, the invention provides a kind of organic acid method in mensuration oil sample, wherein said organic acid molecular weight is less than 180 dalton (Da).Can use electrospray ionization mass spectrum technology, negative ion electrospray spraying mass-spectrometric technique, electron spray Fourier Transform Ion cyclotron Resonance mass-spectrometric technique, negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique or use to be less than the tuning negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique of 200 daltonian molecular weight ranges for molecular weight and carry out described mensuration.Described little molecule acid can be C for chemical formula
nh
2no
2organic acid, wherein n is the total number of carbon atoms.
In one aspect, the invention provides a kind of method being used as with the material of oil surface in contact of determining in crude oil system of processing, described method is based on according to the assay method described in above-mentioned either side.In the operating process of oil processing equipment, describedly can be set to contact such oil material with oil surface in contact, the corrosivity of this oil material is based on described assay method and definite.Can be with the oil material that will contact in the operating process of oil processing equipment with oil surface in contact described in oil sample representative.Oil sample can come from the pilot plant that represents petroleum refining system.In the operating process of oil processing equipment, describedly can be set to contact such oil material with oil surface in contact, the corrosivity of this oil material is based on described assay method and based on obtaining the sample position of oil sample in pilot plant and definite.In the operating process of petroleum refining system, described and oil surface in contact can be the inside surfaces of the pipeline that therefrom passes through of oil material.Described and oil surface in contact can be the inside surface of operating unit, and described operating unit is configured to implement at least a portion process operation in petroleum refining process.
In one aspect, the invention provides a kind of method that adds corrosion inhibiter in petroleum refining system of determining, the method is based on according to the assay method described in above-mentioned either side, and wherein oil sample can be taken from described petroleum refining system.Adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil, and the corrosivity of wherein said oil material is based on described assay method and definite.Or adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil material, the corrosivity of wherein said oil material is based on described assay method and based on obtaining the sample position of oil sample in petroleum refining system and definite.Or adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil material, wherein using the representative of oil sample as described oil material.
In one aspect, the invention provides a kind of method of monitoring extent of corrosion in petroleum refining system of determining, it is characterized in that, the method is based on according to the assay method described in above-mentioned either side, and wherein crude oil sample is taken from described petroleum refining system.In described petroleum refining system to the monitoring of extent of corrosion based on described assay method and definite.Or to the monitoring of extent of corrosion, be based on described assay method and based on obtaining the sample position of oil sample in described petroleum refining system and definite in described petroleum refining system.
In one aspect, the invention provides a kind of assay method of measuring acid compound in oil sample, it comprises the step of measuring the Acid bearing-oxygen compound in described oil sample, and this Acid bearing-oxygen compound is that molecular weight is less than 180 daltonian hydrocarbon oxides.In one embodiment, can use negative ion electrospray spraying mass-spectrometric technique to carry out the mensuration of described hydrocarbon oxide.In one embodiment, can use negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique to carry out the mensuration of described hydrocarbon oxide.In one embodiment, can use for molecular weight and be less than the mensuration that the tuning negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique of 200 daltonian molecular weight ranges is carried out described hydrocarbon oxide.Hydrocarbon oxide of the present invention comprises organic acid, and this organic acid chemical formula is C
nh
2no
2, the integer that wherein n is 2-8.For example, described organic acid is one or more in acetic acid, propionic acid, n-butyric acie, isobutyric acid, valeric acid, caproic acid.
In one aspect, the invention provides a kind of method that prevents oil processing equipment corrosion, described method comprises the steps:, according to the assay method of acid compound in above-mentioned arbitrary mensuration oil sample, to measure the Acid bearing-oxygen compound in oil sample to be processed; The composition of the Acid bearing-oxygen compound based on determined, selection can tolerate the material of this Acid bearing-oxygen compound, as the surperficial material contacting with oil in described oil processing equipment.In one embodiment, described oil processing equipment is crude oil processing equipment.The described surface contacting with oil can be the inside surface of the pipeline that therefrom passes through of oil.Or the described surface contacting with oil is the inside surface of the operating unit in crude oil processing equipment, described operating unit is configured to implement at least a portion process operation in Crude Oil Processing.In one embodiment, above-mentioned arbitrary method that prevents oil processing equipment corrosion also comprises to the step that adds corrosion inhibiter in processed oil.
In one aspect, the invention provides a kind of method that prevents oil processing equipment corrosion, described method comprises the steps: to obtain oil sample in petroleum refining process; According to the assay method of acid compound in above-described arbitrary mensuration oil sample, measure the Acid bearing-oxygen compound in the oil sample of obtaining; The composition of the Acid bearing-oxygen compound based on determined adds the corrosion inhibiter that can make this oil reduce process equipment corrosivity in processed oil.
In one aspect of the method, the invention provides a kind of oil processing equipment, it comprises: sampler, this sampler has the sample tap that obtains processed oil sample from oil processing equipment, the oil sample of obtaining is for implementing the assay method of above-described arbitrary mensuration oil sample acid compound, to measure Acid bearing-oxygen compound wherein; Corrosion inhibiter injection device, this injection device has corrosion inhibiter inlet, for add the corrosion inhibiter that can make this oil reduce process equipment corrosivity to processed oil.In one embodiment, the surperficial material contacting with processed oil in described equipment is selected by the following method: according to the assay method of acid compound in above-described arbitrary mensuration oil sample, measure the Acid bearing-oxygen compound in oil sample to be processed; The composition of the Acid bearing-oxygen compound based on determined, selection can tolerate the material of this Acid bearing-oxygen compound, as the surperficial material contacting with oil in described oil processing equipment.Therefore, the selection of described material is at this stone of preparation
Before oil process equipment, carry out.
Accompanying drawing explanation
Hereinafter with reference to accompanying drawing, describe most preferred embodiment, accompanying drawing comprises:
Fig. 1 is the ESI FT-ICR high resolution mass spectrum figure of the Liaohe River in example 1 (Liaohe) crude oil with high acid value;
Fig. 2 is the ESI FT ICR high resolution mass spectrum figure of Liaohe River crude oil with high acid value after 400 ° of C heat treated in example 2;
Fig. 3 is the ESI FT ICR high resolution mass spectrum figure of Liaohe River crude oil with high acid value after 400 ° of C heat treated in example 2, and it obtains by tuning mass spectrum operating conditions the mass spectrogram that molecular mass is less than 200Da.
Embodiment
The present invention proposes a kind of method of analyzing oil small molecular acidic components, and measures the method that these oil small molecular acid form.
Find that crude oil with high acid value can be converted into the oil product that comprises small molecular organic acid when thermal treatment, these organic acids may bring etching problem in petroleum refining process, monitor these organic acids and contribute to solve the etching problem in Crude Oil Processing.
" oil " of the present invention refers to crude oil and the crude oil through processing or processing through preliminary (or part).
Crude oil is a kind of material that originates from and/or take from the natural hydro carbons compositions of mixtures of hydrocarbon containing formation and the distillation of unprocessed equipment and/or fractionation separates.Crude oil can be cut into by the method for atmospheric distillation/decompression distillation/micro-distillation a plurality of components of different boiling scope.Typical natural materials comprises coal, pitch, oil-sand, or crude oil.
In certain embodiments, for example, oil sample is a crude oil sample of at least processing through part.Processing refers to the variation that comprises that following any one or more property effects form to crude oil here: reduce molecular weight, reduce boiling spread, reduce asphalt content, reduce hydrocarbon number of free radical, or minimizing impurity, as sulphur, nitrogen, oxygen, halogenide and metal etc.
" Acid bearing-oxygen compound " of the present invention refers to and can ionize out hydrionic oxygenatedchemicals, and it can be less than for molecular weight the hydrocarbon oxide of 180Da." Acid bearing-oxygen compound " content in oil sample can for the detectability (as 1ppm) of instrument be to 5000ppm, for example, be 10-1000ppm, or be 50-200ppm." hydrocarbon oxide " refers to the compound that is inserted with one or more oxygen atoms (for example 2 or 3 oxygen atoms) in hydrocarbon molecule formula, and its relative molecular mass (also referred to as molecular mass or molecular weight) can be for being less than 180Da.Described " hydrocarbon oxide " comprises straight or branched or ring-type, saturated or undersaturated organic acid (for example little molecule acid), but is not limited to this.The total number of carbon atoms in described " hydrocarbon oxide " per molecule can be the integer of 2-8, and its example comprises: acetic acid (C
2h
4o
2), propionic acid (C
3h
6o
2), n-butyric acie (n-C
4h
8o
2), isobutyric acid (i-C
4h
8o
2), valeric acid (C
5h
10o
2), caproic acid (C
6h
12o
2), C
2h
4o
3, C
6h
5oH, C
7h
7oH etc.
" little molecule acid " of the present invention refers to that relative molecular mass (referred to as molecular mass or molecular weight) is less than the acid compound of 180Da.In certain embodiments, the relative molecular mass of " little molecule acid " is less than 150Da.In certain embodiments, the relative molecular mass of " little molecule acid " is less than 120Da.
It is with C that the typical case of little molecule acid forms
nh
2no
2for the organic acid of molecular formula general formula, wherein n can be the integer of 2-8.In the acid of instantiation small molecular, comprise acetic acid (C
2h
4o
2), propionic acid (C
3h
6o
2), n-butyric acie (n-C
4h
8o
2), isobutyric acid (i-C
4h
8o
2), valeric acid (C
5h
10o
2) and caproic acid (C
6h
12o
2) etc.
In part embodiment, for example, use the little molecule acid of Electrospray Ionization Mass Spectrometry, for example, electrospray ionization mass spectrum operates at negative ion mode.
In part embodiment, for example, use the little molecule acid of electron spray Fourier Transform Ion cyclotron Resonance mass spectrophotometry, as negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique.
The process of using above various electrospray ionization mass spectrum technology to analyze or measure comprises: (a) oil sample is dissolved in solvent, obtains the solution I that petroleum concentration is 5-20mg/mL; (b) solution I dilution is obtained to the solution II that petroleum concentration is 0.1-0.4mg/mL; (c) in every 1mL solution II, add the ammoniacal liquor of 10-20 μ L to obtain solution III; (d) solution III is carried out to above-mentioned various Electrospray Ionization Mass Spectrometry, for example negative ion electrospray spraying mass-spectrometric technique, negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique or be less than the tuning negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique of 200 daltonian molecular weight ranges for molecular weight.Wherein, (a) in solvent used can be little molecule weak polar organic solvent, such as cyclohexane, benzene, toluene, methylene chloride etc.; (b) in, dilution thinning agent used can be the fused solution of polar solvent and low pole/non-polar solvent, and the polar solvent here can be methyl alcohol, acetonitrile etc., and the low pole/non-polar solvent here can be benzene, toluene, cyclohexane, methylene chloride etc.; (c) in, the concentration range of ammoniacal liquor used is 20-30%(volume ratio v/v).
In part embodiment, for example, analytical approach comprises: (a) oil sample is dissolved in toluene and obtains solution I, (b) (in mixed solution, the volume ratio scope of toluene and methyl alcohol is 1:0.5 – 1:5 to use toluene and methanol mixed solution, as 1:3) dilute solution I obtains solution II, (c) in solution II, add ammoniacal liquor to obtain solution III, the concentration range of ammoniacal liquor is 20-30%(v/v), (d) solution III is carried out to negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass spectrum (ESI FT-ICR MS) analysis.
In part embodiment, for example, oil sample concentration is 5-20mg/mL in solution I.In certain embodiments, for example, solution I is mixed with the ratio that toluene and methanol solution is 1:2-1:5 according to volume ratio.In certain embodiments, for example, the concentration of oil sample in solution II is 0.1-0.4mg/mL.In certain embodiments, for example, the addition that adds the ammoniacal liquor in 1mL solution II is 10-20 μ L.
Usually, the superconducting magnet of ESI FT-ICR MS configuration 9.4T.
In certain embodiments, for example, based on according to the mensuration described in arbitrary embodiment in all embodiment recited above (or analysis), can determine the material being used as with oil surface in contact in petroleum refining system.In some embodiment in these embodiments, for example, be describedly set to contact such oil material with oil surface in contact, the corrosive attack of this oil material (corrosivity) is based on described mensuration and definite.In certain embodiments, for example, oil sample has represented the described oil material that will contact in the operating process of oil processing equipment with oil surface in contact.In certain embodiments, for example, oil sample comes from the pilot plant that represents petroleum refining system.In certain embodiments, for example, describedly be set to contact such oil material with oil surface in contact, the corrosive attack of this oil material (corrosivity) is based on described mensuration and based on obtaining the sample position of this oil sample in pilot plant and definite.In certain embodiments, for example, described and oil surface in contact are the inside surfaces of the pipeline that therefrom passes through of oil, and it is set to contact oil in the operating process of petroleum refining system.In certain embodiments, for example, described and oil surface in contact is the inside surface of operating unit (for example distilling unit), and described operating unit is configured to implement at least a portion process operation in petroleum refining process.
Of the present inventionly for the vessel surface material contacting with oil, comprise carbon steel, stainless steel and alloy.
In certain embodiments, for example, based on according to the mensuration described in arbitrary embodiment above (or analysis), can determine and in petroleum refining process, add corrosion inhibiter, wherein, analytic process oil sample used is taken from this petroleum refining process.In certain embodiments, for example, the object that adds corrosion inhibiter is the corrosive attack causing in order to reduce oil material, and wherein the corrosivity of this oil material is based on described mensuration and definite.In certain embodiments, for example, adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil material, and wherein the corrosivity of this oil material is based on described mensuration and based on obtaining the sample position of this oil sample in petroleum refining system and definite.In certain embodiments, for example, adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil material, wherein usings the representative of oil sample as this oil material.
The example of corrosion inhibiter of the present invention comprises tributyl phosphate, alkyl phenol sulfonate (wherein the carbon atom number range of alkyl is C8-C18) or their potpourri or has the material of identity function with these materials.
In certain embodiments, for example, based on according to the mensuration described in arbitrary embodiment above (or analysis), can determine the indication of monitoring extent of corrosion in petroleum refining system, wherein, for the oil sample of analyzing, take from the oil after this petroleum refining system processing.In certain embodiments, for example, in petroleum refining system to the monitoring of extent of corrosion based on described mensuration and definite.In certain embodiments, for example, in petroleum refining system, to the monitoring of extent of corrosion, be based on organic acid being measured and based on obtaining the sample position of this oil sample in petroleum refining system and definite.In certain embodiments, for example, in petroleum refining process, to the monitoring of extent of corrosion, can comprise one or more that use in following means: ultrasound wave, radioactive ray, orientation involves electromagnetic wave.
In certain embodiments, for example, relate to that the statement used of a certain characteristic " is determined based on described mensuration " or similarly expression way refer to: the engineering based on known and the principles of science, the characteristic of being inferred by described mensuration.For example, the mensuration that in technological process, the corrosivity of a certain position can be based on to another location be done in this technological process, by measured corrosivity extrapolation is determined, wherein to consider between the operation between them, comprise between the material input and output between them and between the energy input and output between them.
In certain embodiments, for example, relate to that " monitoring " statement used " is determined based on described mensuration " or similarly expression way refer to: and nonessential monitoring in the position that obtains sample (but also not getting rid of such monitoring mode), but can based on described mensuration, think that most suitable another location monitors, described " based on " comprise engineering and the principles of science based on known, the a certain position of being determined by done mensuration extrapolation, wherein to consider between the operation between them, comprise between the material input and output between them, and between the energy input and output between them.
Hereinafter with reference to nonrestrictive example, embodiment of the present invention are described in more detail.
Embodiment 1
Taking from carbon content in Chinese Liaohe Oil Field crude oil (high TAN) is 86.87%, and hydrogen richness is 11.82%, and sulfur content is 0.30%, and nitrogen content is 0.65%, and oxygen content is 0.85%, is all weight percentage.Using this crude oil as analytic target, the TAN of this sample is 4.56 through methods analyst described in ASTM D664, and these data mean that this crude oil is high TAN crudes.
First this sample is dissolved in and in toluene, obtains 10mg/mL(oil/solvent) solution I.With 20 μ L toluene and methanol mixed solutions (1:3, v/v), by solution I dilution, be 0.2mg/mL(oil/solvent) solution II.By solution II and 15 μ L ammoniacal liquor (NH
4oH, concentration is 25%) be mixed to get solution III.ESI FT-ICR MS by solution III for negative ion mode analyzes.ESI FT-ICR MS is with the superconducting magnet of 9.4T.Fig. 1 is the ESI FT-ICR MS high resolution mass spectrum figure of this high TAN value crude oil sample.Data have shown that in sample, the existence of part oxygenatedchemicals is organic acid.Data have also shown the existence of nitrogen-containing compound in sample.
Embodiment 2
By described in embodiment 1, take from Chinese Liaohe Oil Field crude oil (high TAN) after bakingout process for organic acid analysis.Heat treatment process is: 100mL crude oil is joined in the autoclave of 500mL with stirrer, electric heating cover, water condenser and airbag, wherein stirrer is for the material in stirred autoclave, electric heating cover is for heating the material in reactor, and water condenser is for the liquid reacting product of cooling volatilization.Under stirring, system is warmed up to 400 degrees Celsius, is incubated 1 hour.The gaseous product that reaction is produced is collected in airbag for gas chromatographic analysis.After having tested, the product liquid that reaction is obtained carries out analyzing described in ASTM D664 after being cooled to room temperature.
The product liquid sample that reaction obtains is after process analysis procedure analysis described in ASTM D664, and obtaining its TAN value is 0.73.Heat treatment process causes the great variety (being reduced to 0.73 from 4.56) of crude oil TAN value can think what the decarboxylation reaction of organic acid course of reaction caused.In course of reaction, the generation of organic acid and the hydro carbons decomposition reaction when high temperature also can show from the data from gas chromatography of gaseous reaction product, and gas chromatographic analysis indicates CO, CO
2, C
1-C
4the existence of gas and hydrogen.
The ESI FT-ICR MS that reacted product liquid sample is carried out under negative ion mode analyzes, to measure its acid content.Reacted product liquid sample is dissolved in and in toluene, obtains 10mg/mL(oil/solvent) solution I.With 20 μ L toluene and methanol mixed solutions (1:3, v/v), by solution I dilution, be 0.2mg/mL(oil/solvent) solution II.By solution II and 15 μ L ammoniacal liquor (NH
4oH, concentration is 25%) be mixed to get solution III.ESI FT-ICR MS by solution III for negative ion mode analyzes.ESI FT-ICR MS is with the superconducting magnet of 9.4T.Fig. 2 is the ESI FT-ICR MS high resolution mass spectrum figure through 400 ℃ of heat treated high TAN value LIAOHE CRUDE samples.Compared to Figure 1, in Fig. 2, data show through the reacted petroleum products of bakingout process, and its compound molecule is less than the compound molecule in reactant feed, and hardly containing the oxygenatedchemicals that comprises organic acid.Yet, when follow the trail of minute period of the day from 11 p.m. to 1 a.m of (molecular weight is less than 200Da) within the scope of low-molecular-weight by tuning ESI FT-ICR MS mass spectrum operating conditions analysis, there is unexpected result.Fig. 3, for through 400 ° of heat treated high TAN value LIAOHE CRUDE samples of C ESI FT-ICR MS high resolution mass spectrum figure of (molecular weight is less than 200Da) within the scope of low-molecular-weight, has shown small molecular organic acid---C in figure
2-C
8organic acid exists, and various organic acid content is respectively (ppm): acetic acid 8.2; Propionic acid 5.0; Isobutyric acid 1.2; Butyric acid 1.9; Valeric acid 1.1; Caproic acid 0.3, C
2-C
8organic acid be considered to highly corrosive material and can cause corrosion to the equipment of Crude Oil Processing.The scientific discovery being obtained by method of the present invention shown, in petroleum crude oil, most organic acid decomposes in heat treatment process, yet the small molecular organic acid of trace may be that the decomposed due to macromolecule organic acid obtains.These highly corrosive small molecular organic acids that produce in high TAN value crude oil is heat-treated to process are key factors that refinery etching problem produces.
Embodiment of the present invention is in order more clearly to explain useful effect of the present invention, but can not therefore limit to scope of the present invention.Those skilled in the art, after reading this instructions, obviously can carry out various changes to exemplary embodiment of the present invention and other embodiments.Claims contain such change or embodiment.
Claims (21)
1. measure an organic acid method in oil sample, it is characterized in that described organic acid molecular weight is less than 180 dalton.
2. assay method according to claim 1, is wherein used electrospray ionization mass spectrum technology to carry out described mensuration.
3. assay method according to claim 1, is wherein used negative ion electrospray spraying mass-spectrometric technique to carry out described mensuration.
4. assay method according to claim 1, is wherein used electron spray Fourier Transform Ion cyclotron Resonance mass-spectrometric technique to carry out described mensuration.
5. assay method according to claim 1, is wherein used negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique to carry out described mensuration.
6. assay method according to claim 1, is wherein used for molecular weight, to be less than the tuning negative ion electrospray spraying Fourier Transform Ion cyclotron Resonance mass-spectrometric technique of 200 daltonian molecular weight ranges and to carry out described mensuration.
7. according to the assay method described in any one in claim 1 to 6, wherein said little molecule acid for chemical formula be C
nh
2no
2organic acid, wherein n is the total number of carbon atoms.
8. determine the method being used as with the material of oil surface in contact in crude oil system of processing, it is characterized in that described method is based on according to the assay method described in any one in claim 1 to 7.
9. method according to claim 8, wherein in the operating process of oil processing equipment, is describedly set to contact such oil material with oil surface in contact, and the corrosivity of this oil material is based on described assay method and definite.
10. method according to claim 8, wherein, with the oil material that will contact in the operating process of oil processing equipment with oil surface in contact described in oil sample representative.
Method in 11. according to Claim 8-10 described in any one, wherein, oil sample comes from the pilot plant that represents petroleum refining system.
12. methods according to claim 8, wherein, in the operating process of oil processing equipment, describedly be set to contact such oil material with oil surface in contact, the corrosivity of this oil material is based on described assay method and based on obtaining the sample position of oil sample in pilot plant and definite.
13. according to the method described in any one in claim 7-12, and wherein, in the operating process of petroleum refining system, described and oil surface in contact are the inside surfaces of the pipeline that therefrom passes through of oil material.
14. according to the method described in any one in claim 7-12, and wherein, described and oil surface in contact is the inside surface of operating unit, and described operating unit is configured to implement at least a portion process operation in petroleum refining process.
Determine the method that adds corrosion inhibiter in petroleum refining system for 15. 1 kinds, it is characterized in that, the method is based on according to the assay method described in any one in claim 1-7, and wherein oil sample is taken from described petroleum refining system.
16. methods according to claim 15, wherein, adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil, the corrosivity of wherein said oil material is based on described assay method and definite.
17. methods according to claim 15, wherein, adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil material, and the corrosivity of wherein said oil material is based on described assay method and based on obtaining the sample position of oil sample in petroleum refining system and definite.
18. methods according to claim 15, wherein, adding of corrosion inhibiter is the corrosive attack causing in order to reduce oil material, wherein usings the representative of oil sample as described oil material.
Determine the method for monitoring extent of corrosion in petroleum refining system for 19. 1 kinds, it is characterized in that, the method is based on according to the assay method described in any one in claim 1-7, and wherein crude oil sample is taken from described petroleum refining system.
20. methods according to claim 19, wherein, in described petroleum refining system to the monitoring of extent of corrosion based on described assay method and definite.
21. methods according to claim 19 wherein, are based on described assay method and based on obtaining the sample position of oil sample in described petroleum refining system and definite to the monitoring of extent of corrosion in described petroleum refining system.
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