CN109668971B - Acid-hydrocarbon ratio analysis and gas chromatography sample injection device and method for alkylation reaction product and gas chromatography analysis equipment - Google Patents
Acid-hydrocarbon ratio analysis and gas chromatography sample injection device and method for alkylation reaction product and gas chromatography analysis equipment Download PDFInfo
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Abstract
The invention relates to the field of analysis of alkylation reaction products, and discloses an acid-hydrocarbon ratio analysis and gas chromatography sample injection device and method for the alkylation reaction products and gas chromatography analysis equipment for the alkylation reaction products. The device comprises: a tank (a), a measuring tube (b) with a scale, an acid-hydrocarbon separator (c) filled with a coalescing filler (11), and a holder (d) supporting the tank (a); wherein, the storage tank (a) and the measuring pipe (b) are vertically arranged in parallel and are communicated with each other through an upper pipeline (3) and a lower pipeline (4); a sampling port (7) with the horizontal height higher than that of the lower pipeline (4) is arranged on the side wall of the storage tank (a); the acid hydrocarbon separator (c) is communicated with a sampling port (7) through a sampling pipeline (5) with a sampling valve (10), and the coalescence packing (11) is used for separating acid and hydrocarbon in the alkylation reaction product from the storage tank (a). The acid to hydrocarbon ratio can be determined and the acid is avoided from entering the chromatogram.
Description
Technical Field
The invention relates to the field of analysis of alkylation reaction products, in particular to an acid-hydrocarbon ratio analysis and gas chromatography sample injection device for alkylation reaction products, a method for acid-hydrocarbon ratio analysis and gas chromatography sample injection by using the device, and gas chromatography analysis equipment using the device as a sampler.
Background
The alkylation reaction of isoalkane and olefin mainly refers to the alkylation reaction of isobutane and butene, and the reaction process is an organic addition reaction of alkane molecules to olefin molecules in the presence of an acidic catalyst. Alkylation is an important process in the petrochemical industry.
Iso-C generated by reaction of isobutane and butene under action of strong acid catalyst8Alkanes, known as alkylated gasolines. The alkylated gasoline has the characteristics of high octane number (RON94-96), low Reid vapor pressure, extremely low sulfur content and olefin content, no benzene and aromatic hydrocarbon, and is an excellent gasoline blending component. The gasoline blended by the alkylated gasoline and the new formula is used as the fuel of the gasoline engine, so that the urban air pollution caused by the emission of the gasoline tail gas can be greatly alleviated. In this sense, alkylate gasoline is an environmentally friendly petrochemical product.
At present, the catalyst adopted in the industrial alkylation reaction is mainly concentrated sulfuric acid or hydrofluoric acid and other liquid strong acids. Typical alkylation reaction processes still employ either horizontal stirred tank reactors or tubular reactors.
CN2790575Y discloses a horizontal alkylation reactor, including motor (11), propeller agitator (10), casing (5), cooling tube bank (4), coolant liquid entry (1), coolant liquid export (2), raw materials inlet (9), circulation acid entry (12), reactant and acid export (3), wherein, motor (11) remaining propeller agitator (10) are direct to be connected, be equipped with inner shell (7) in casing (5), raw materials inlet (9) and circulation acid entry (12) are let in inner shell (7), cooling tube bank (4) are in inner shell (7).
US3281213A discloses a vertical alkylation reactor, the main body of which is a riser connected to a horizontal tank, the horizontal tank is filled with an acid hydrocarbon emulsion, isoparaffin and olefin participating in the reaction are injected through a nozzle at the bottom of the riser, the acid hydrocarbon emulsion in the horizontal tank is driven by the attraction force caused by the injection to enter the riser, and the reaction is carried out in the riser reactor. The top end of the lifting pipe is connected with a separation tank for separating reaction products. The separated acid hydrocarbon emulsion is circulated into the horizontal tank at the bottom of the lifting pipe. However, the mixing of the acid hydrocarbon emulsion with the other reactants in the riser is not satisfactory, and in addition, the entire reactor system using one riser, two horizontal tanks and one downcomer is bulky and not compact.
The acid to hydrocarbon ratio is an important control parameter for alkylation reactions during alkylation reactions. In the actual industrial production or experimental process, the acid-hydrocarbon ratio of the materials in the reactor needs to be monitored in real time, and the alkylation product is subjected to gas chromatography under the condition of pressure, and the product is mixed with acid.
The prior art does not provide an ideal means for determining the acid to hydrocarbon ratio of the materials in the alkylation reactor and for feeding the acid-containing alkylation reaction product to the gas chromatograph.
Disclosure of Invention
The invention aims to solve the problems of how to realize the sample injection of an alkylation reaction product into a gas chromatograph and ideally determine the acid-hydrocarbon ratio of materials in the alkylation reactor, and provides an acid-hydrocarbon ratio analysis and gas chromatography sample injection device and method for the alkylation reaction product and a gas chromatography analysis device.
The inventor of the invention finds that the conventional gas chromatograph cannot directly sample the alkylation reaction product in the process of researching the alkylation reaction, and the phenomena of corrosion of a high-pressure sample injection valve and blockage of a gas circuit often exist. In addition, during traditional sampling, the problem that acid-containing liquefied gas splashes out exists, and personal injury and environmental pollution are caused to analysts. In view of this, the inventors propose the present invention to overcome the above problems.
In order to achieve the above object, the present invention provides in a first aspect an apparatus for analyzing acid-to-hydrocarbon ratio of alkylation reaction product and for introducing gas chromatography sample, comprising: a tank a, a measuring pipe b with a scale, an acid-hydrocarbon separator c filled with a coalescing filler 11, and a support d supporting the tank a; wherein the content of the first and second substances,
the storage tank a and the measuring pipe b are vertically arranged in parallel, the upper pipeline 3 is communicated with the upper ends of the storage tank a and the measuring pipe b, and the lower pipeline 4 is communicated with the lower ends of the storage tank a and the measuring pipe b;
the bottom end of the storage tank a is communicated with a feeding pipeline 2 with an inlet valve 8, and the top end of the storage tank a is communicated with a discharging pipeline 1 with an outlet valve 9; a sampling port 7 with the horizontal height higher than that of the lower pipeline 4 is arranged on the side wall of the storage tank a;
the acid hydrocarbon separator c is communicated with a sampling port 7 through a sampling pipeline 5 with a sampling valve 10, and the coalescing packing 11 is used for separating acid and hydrocarbon in the alkylation reaction product from the storage tank a; the acid hydrocarbon separator c is provided with a feed line 6 for withdrawing hydrocarbons separated by the coalescing packing 11.
Preferably, the vertical height of the lower pipeline 4 from the lower end of the storage tank a is 1/20-1/10 of the height of the storage tank a; the vertical height of the upper pipeline 3 from the upper end of the storage tank a is 1/20-1/10 of the height of the storage tank a.
Preferably, the vertical height of the sampling port 7 from the lower end of the storage tank a is 1/4-1/3 of the height of the storage tank a.
Preferably, the ratio of the cross-sectional area of the acid-hydrocarbon separator c to the cross-sectional area of the sampling line 5 is (1 to 50): 1.
preferably, the acid hydrocarbon separator c is a cylindrical vessel, and the ratio of the height to the inner diameter of the acid hydrocarbon separator c is 1: (2-20).
Preferably, the coalescing filler is selected from at least one of stainless steel mesh, polytetrafluoroethylene ribbons, glass wool fibers and polypropylene filaments.
In a second aspect, the present invention provides a method for analyzing acid-hydrocarbon ratio of alkylation reaction product and introducing gas chromatography sample, comprising:
(i) using the apparatus of the present invention to remove a sample containing acid and hydrocarbon from an alkylation reactor;
(ii) the device containing the taken sample is kept still, the layering of acid and hydrocarbon is shown in a measuring pipe b, and the volume ratio of acid and hydrocarbon in the sample is determined from a scale corresponding to the measuring pipe b;
(iii) opening the outlet valve 9 to discharge acid, and closing the outlet valve 9 to stop discharging acid when the layered liquid level in the measuring pipe b is reduced to a position between the sampling port 7 and the lower pipeline 4;
(iv) opening a sampling valve 10, introducing hydrocarbon mixed with a small amount of acid above a sampling port 7 in the device into an acid-hydrocarbon separator c through a sampling pipeline 5, separating acid through a coalescence packing 11, and obtaining hydrocarbon for gas chromatographic analysis from a sample introduction pipeline 6.
Preferably, the process of taking out said sample in step (i) comprises: the apparatus was connected in parallel with the alkylation reactor via outlet line 1 and feed line 2; opening inlet valve 8 and outlet valve 9 to fill the apparatus with alkylation reaction product containing acid and hydrocarbons in the alkylation reactor; the inlet valve 8 and the outlet valve 9 are closed and separated from the alkylation reactor.
In a third aspect, the present invention provides an apparatus for gas chromatography of an alkylation reaction product, comprising a gas chromatograph and the apparatus of the present invention, the apparatus being in communication with the gas chromatograph via a sample injection line 6.
By adopting the technical scheme, the acid-hydrocarbon ratio of the materials in the alkylation reactor can be more conveniently determined.
In the device provided by the invention, the position of the set sampling port is higher than the lowest end of the storage tank and the lower pipeline, so that acid and hydrocarbon are layered, and acid liquid can be prevented from being carried when the hydrocarbon positioned on the upper layer is discharged. And free acid carried in the hydrocarbon phase can be removed by the separation of the coalescent filler, thereby avoiding the corrosion of a chromatographic high-pressure sample injection valve and the blockage of a chromatographic sample injection gas circuit.
When acid discharging operation is performed, acid liquor discharging is limited to meet the condition that the layered liquid level is lowered between the sampling port and the lower pipeline, acid-containing liquefied gas does not need to be discharged, coalesced filling materials are used for removing the acid-containing liquefied gas contained in the hydrocarbon in an auxiliary mode, and the defects that the acid-containing liquefied gas splashes out to cause personal injury and environmental pollution to operating personnel are overcome.
Drawings
FIG. 1 is a schematic view of an apparatus provided by the present invention;
FIG. 2 is a schematic illustration of an acid hydrocarbon separator c filled with coalescing packing 11 in an apparatus provided by the present invention.
Description of the reference numerals
a. Storage tank b, measuring pipe c and acid hydrocarbon separator
d. Support 1, discharging pipeline 2, charging line
3. Upper pipeline 4, lower pipeline 5 and sampling pipeline
6. Sample introduction pipeline 7, sampling port 8 and inlet valve
9. The outlet valve 10, the sampling valve 11 and the coalescent filler
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides an apparatus for analyzing acid-to-hydrocarbon ratio of alkylation reaction product and sampling gas chromatography, as shown in fig. 1, comprising: a tank a, a measuring pipe b with a scale, an acid-hydrocarbon separator c filled with a coalescing filler 11, and a support d supporting the tank a; wherein the content of the first and second substances,
the storage tank a and the measuring pipe b are vertically arranged in parallel, the upper pipeline 3 is communicated with the upper ends of the storage tank a and the measuring pipe b, and the lower pipeline 4 is communicated with the lower ends of the storage tank a and the measuring pipe b;
the bottom end of the storage tank a is communicated with a feeding pipeline 2 with an inlet valve 8, and the top end of the storage tank a is communicated with a discharging pipeline 1 with an outlet valve 9; a sampling port 7 with the horizontal height higher than that of the lower pipeline 4 is arranged on the side wall of the storage tank a;
the acid hydrocarbon separator c is communicated with a sampling port 7 through a sampling pipeline 5 with a sampling valve 10, and the coalescing packing 11 is used for separating acid and hydrocarbon in the alkylation reaction product from the storage tank a; the acid hydrocarbon separator c is provided with a feed line 6 for withdrawing hydrocarbons separated by the coalescing packing 11.
In the present invention, storage tank a is used to store material withdrawn from the alkylation reactor with acid and alkylation reaction product hydrocarbons. The acid can be a catalyst used in alkylation reaction, and can be concentrated sulfuric acid, strong acidic ionic liquid or mixed acid mainly containing concentrated sulfuric acid. The storage tank a can be a pressure-resistant steel cylinder and can contain materials comprising liquefied gases such as propane, butane and the like. Preferably, the storage tank a has an inner diameter of 1 to 20cm and a height of 10 to 100 cm.
In the invention, the inlet valve 8 and the outlet valve 9 are used for controlling the feeding and the discharging of acid liquor to the storage tank a, an acid-proof stop valve with a valve core can be adopted, and the valve core can be made of polytetrafluoroethylene, 316L steel, 904L steel, Alloy20 or Hastelloy, preferably 904L stainless steel.
In the present invention, the measuring tube b is made of a transparent material, and may be made of a pressure-resistant boronized glass, a quartz tube, a pressure-resistant transparent polytetrafluoroethylene tube, or the like, and preferably a pressure-resistant transparent polytetrafluoroethylene tube. The transparent material of the measuring area b is provided with a scale which can be used for reading the volume ratio between the lower layer acid liquid and the upper layer hydrocarbon gas separated by standing and layering the material taken out from the alkylation reactor in the storage tank a, namely the acid-hydrocarbon ratio of the material. Preferably, the measuring tube b has an inner diameter of 0.1-2 cm and a height of 10-100 cm.
In the present invention, upper line 3 and lower line 4 communicate with storage tank a and measurement pipe b, which allows measurement of the acid-to-hydrocarbon ratio of the material withdrawn from the alkylation reactor in storage tank a. Preferably, the vertical height of the lower pipeline 4 from the lower end of the storage tank a is 1/20-1/10 of the height of the storage tank a; the vertical height of the upper pipeline 3 from the upper end of the storage tank a is 1/20-1/10 of the height of the storage tank a.
In the present invention, the inner diameter of the measurement pipe b is smaller than the inner diameter of the reservoir a. Preferably, the inner diameter ratio of the storage tank a to the measuring pipe b is (10-20): 1.
in the present invention, the sampling port 7 is used to introduce the residual hydrocarbons after the alkylation reaction product in the storage tank a is drained into the acid-hydrocarbon separator c filled with the coalescence packing 11. The sampling port 7 is arranged on the side wall of the storage tank a, the vertical height of the sampling port is higher than that of the lower pipeline 4, so that when acid liquid is discharged, when the layered interface of the acid liquid and hydrocarbon in the measuring pipe b is observed to fall between the sampling port 7 and the lower pipeline 4, the acid liquid discharge is stopped, the hydrocarbon part (containing a small amount of vaporized acid) can be ensured to be taken by the sampling port 7, the liquid acid discharge is always ensured to be carried out when the acid liquid is discharged, and the harm of splashing caused by discharging acid-containing hydrocarbon gas (containing acid) during the acid liquid discharge is avoided. That is, the height of the sampling port 7 relative to the lower line 4 ensures sampling of hydrocarbons and also simplifies the requirements for acid removal. Preferably, the vertical height of the sampling port 7 from the lower end of the storage tank a is 1/4-1/3 of the height of the storage tank a.
In the present invention, the hydrocarbon sample obtained from the sampling port 7 may also contain a small amount of acid gas, and further the hydrocarbon and the acid are separated by the coalescing packing 11 filled in the acid-hydrocarbon separator c. Preferably, the ratio of the cross-sectional area of the acid-hydrocarbon separator c to the cross-sectional area of the sampling line 5 is (1 to 50): 1, preferably (10-20): 1. the hydrocarbon sample in sampling line 5 can be made to better diffuse into contact with coalescing packing 11 as it enters acid hydrocarbon separator c, more efficiently separating out the acid.
In the present invention, the acid-hydrocarbon separator c is shaped to facilitate the diffusion and contact between the acid and the hydrocarbon in the coalescing packing 11, thereby separating the acid and the hydrocarbon more effectively. Preferably, the acid hydrocarbon separator c is a cylindrical vessel, and the ratio of the height to the inner diameter of the acid hydrocarbon separator c is 1: (2-20); preferably 1: (5-10). The inner diameter of the acid hydrocarbon separator c is the diameter of the bottom surface of the acid hydrocarbon separator c. The sampling pipeline 5 and the sample injection pipeline 6 are respectively communicated with the centers of two opposite bottom surfaces of the acid hydrocarbon separator c.
In the invention, the coalescence packing 11 filled in the acid hydrocarbon separator c realizes the separation of the hydrocarbon sample from the sampling port 7, and ensures that the separated hydrocarbon can be led out from the sample injection pipeline 6 and is used for the sample injection of a gas phase analyzer. Preferably, the coalescing filler is selected from at least one of stainless steel mesh, polytetrafluoroethylene ribbons, glass wool fibers and polypropylene filaments. Preferably, the coalescing filler 11 is fiberglass fibers, which may be of known and commercially available nature. For example, the CR17-2400 diameter of WU lake Baiyun glass fiber Limited is 17-24 μm.
In a second aspect, the present invention provides a method for analyzing acid-hydrocarbon ratio of alkylation reaction product and introducing gas chromatography sample, comprising:
(i) using the apparatus of the present invention to remove a sample containing acid and hydrocarbon from an alkylation reactor;
(ii) the device containing the taken sample is kept still, the layering of acid and hydrocarbon is shown in a measuring pipe b, and the volume ratio of acid and hydrocarbon in the sample is determined from a scale corresponding to the measuring pipe b;
(iii) opening the outlet valve 9 to discharge acid, and closing the outlet valve 9 to stop discharging acid when the layered liquid level in the measuring pipe b is reduced to a position between the sampling port 7 and the lower pipeline 4;
(iv) opening a sampling valve 10, introducing hydrocarbon mixed with a small amount of acid above a sampling port 7 in the device into an acid-hydrocarbon separator c through a sampling pipeline 5, separating acid through a coalescence packing 11, and obtaining hydrocarbon for gas chromatographic analysis from a sample introduction pipeline 6.
In the present invention, preferably, the process of taking out the sample in step (i) comprises: the apparatus was connected in parallel with the alkylation reactor via outlet line 1 and feed line 2; opening inlet valve 8 and outlet valve 9 to fill the apparatus with alkylation reaction product containing acid and hydrocarbons in the alkylation reactor; the inlet valve 8 and the outlet valve 9 are closed and separated from the alkylation reactor.
In the present invention, the standing in step (ii) may be performed by placing the apparatus containing the taken-out sample on the ground with a support d, and vertically placing the storage tank a for 1 to 20 hours, preferably 4 to 8 hours, so that the acid and the hydrocarbon contained in the sample are sufficiently layered. Typically the lower layer is acid and the upper layer is hydrocarbon. The acid can be concentrated sulfuric acid, strongly acidic ionic liquid or mixed acid mainly containing concentrated sulfuric acid. The hydrocarbon may comprise isobutane, C3-C5Olefins and isobutane and C3-C5The alkylation reaction product of olefins.
In a third aspect, the present invention provides an apparatus for gas chromatography of an alkylation reaction product, comprising a gas chromatograph and the apparatus of the present invention, the apparatus being in communication with the gas chromatograph via a sample injection line 6.
The present invention will be described in detail below by way of examples.
In the following examples, the acid content of the sample before the sample introduction by the gas chromatograph was measured by an acid-base titration method.
Example 1
The apparatus shown in fig. 1, wherein,
the storage tank a is a pressure-resistant steel cylinder with the inner diameter of 5cm and the height of 40 cm; the measuring tube b was a transparent pressure-resistant polytetrafluoroethylene tube with a scale having an inner diameter of 1cm and a height of 30 cm. The inner diameter ratio of the storage tank a to the measuring pipe b is 10: 1. the upper pipeline and the lower pipeline are communicated between the storage tank a and the measuring pipe b. The support d supports the storage tank a to be vertically placed. The vertical distance of the upper and lower pipelines from the upper and lower ends of the storage tank a, respectively, is 1/20 the height of the storage tank a.
The sampling port is arranged on the side wall of the storage tank a, and the vertical height from the lower end of the storage tank a is 1/3 the height of the storage tank a.
The acid hydrocarbon separator c is a cylindrical container, the ratio of the height to the inner diameter is 1:5, the inner diameter is 8cm, and the height is 1.6 cm; the glass fiber is filled with glass fiber (CR 17-2400 glass fiber of WU lake Baiyun glass fiber Co., Ltd.) with diameter of 17-24 μm. The lower end of the acid hydrocarbon separator c communicates with the sampling port via a sampling line 5 having a diameter of 0.6cm, and the ratio of the cross-sectional area of the acid hydrocarbon separator c to the cross-sectional area of the sampling line 5 is 15: 1.
the device is connected with an alkylation reactor in parallel, and an inlet valve (904L stainless steel valve core) on a feed pipeline is opened to add an alkylation reaction product; the outlet valve (904L stainless steel spool) on the outlet line was opened to allow the alkylation reaction product to fill the apparatus. And closing the inlet valve and the outlet valve, obtaining a sample, separating the device for obtaining the alkylation reaction product from the alkylation reactor, and standing for 8 hours.
The samples in the device are layered, the lower layer is acid liquor, and the upper layer is hydrocarbon. The acid-hydrocarbon volume ratio in the sample was determined to be 1:1 by observing through the measurement pipe b and by a scale on the measurement pipe b.
And opening an outlet valve to discharge the acid liquor. The drop in acid hydrocarbon stratification interface was observed through the measurement tube b. And when the layering interface is lower than the sampling port, closing the discharge valve to stop discharging acid. And (4) standing the device, then opening a sampling valve, discharging the hydrocarbon containing the acid gas on the upper layer remained in the storage tank from a sampling port, and entering an acid hydrocarbon separator c through a sampling pipeline. And under the separation action of the coalescence packing, discharging the hydrocarbon sample from which the acid gas is separated out from the sample injection pipeline, measuring the acid content of the hydrocarbon sample, and feeding the hydrocarbon sample into a gas chromatograph for analysis.
The acid content of the hydrocarbon sample was 20 ppm.
And (4) performing multiple times of hydrocarbon sample chromatographic analysis, wherein the chromatographic high-pressure sample injection valve has no corrosion phenomenon, and the chromatographic sample injection gas circuit is not blocked.
Example 2
The apparatus shown in fig. 1, wherein,
the storage tank a is a pressure-resistant steel cylinder with the inner diameter of 2cm and the height of 90 cm; the measuring tube b was a transparent pressure-resistant polytetrafluoroethylene tube with a scale having an inner diameter of 0.5cm and a height of 80 cm. The inner diameter ratio of the storage tank a to the measuring pipe b is 20: 1. the upper pipeline and the lower pipeline are communicated between the storage tank a and the measuring pipe b. The support d supports the storage tank a to be vertically placed. The vertical distance of the upper and lower pipelines from the upper and lower ends of the storage tank a, respectively, is 1/10 the height of the storage tank a.
The sampling port is arranged on the side wall of the storage tank a, and the vertical height from the lower end of the storage tank a is 1/4 the height of the storage tank a.
The acid hydrocarbon separator c is a cylindrical container, the ratio of the height to the inner diameter is 1:10, the inner diameter is 3cm, and the height is 0.3 cm; in which glass wool fibers (CR 27-2400. mu.m diameter glass wool fibers from WU lake Baiyun glass fiber Co., Ltd.) were filled. The lower end of the acid hydrocarbon separator c is communicated with a sampling port through a sampling pipeline 5, the diameter of the sampling pipeline is 1cm, and the ratio of the cross-sectional area of the acid hydrocarbon separator c to the cross-sectional area of the sampling pipeline 5 is 10: 1.
the device is connected with an alkylation reactor in parallel, and an inlet valve (904L stainless steel valve core) on a feed pipeline is opened to add an alkylation reaction product; the outlet valve (904L stainless steel spool) on the outlet line was opened to allow the alkylation reaction product to fill the apparatus. And closing the inlet valve and the outlet valve, obtaining a sample, separating the device for obtaining the alkylation reaction product from the alkylation reactor, and standing for 4 hours.
The samples in the device are layered, the lower layer is acid liquor, and the upper layer is hydrocarbon. The volume ratio of acid to hydrocarbon in the sample was determined by observing through the measuring tube b and from a scale on the measuring tube b, 2: 1.
and opening an outlet valve to discharge the acid liquor. The drop in acid hydrocarbon stratification interface was observed through the measurement tube b. And when the layering interface is lower than the sampling port, closing the discharge valve to stop discharging acid. And (4) standing the device, then opening a sampling valve, discharging the hydrocarbon containing the acid gas on the upper layer remained in the storage tank from a sampling port, and entering an acid hydrocarbon separator c through a sampling pipeline. And under the separation action of the coalescence packing, discharging the hydrocarbon sample from which the acid gas is separated out from the sample injection pipeline, measuring the acid content of the hydrocarbon sample, and feeding the hydrocarbon sample into a gas chromatograph for analysis.
The acid content of the hydrocarbon sample was 50 ppm.
And (4) performing multiple times of hydrocarbon sample chromatographic analysis, wherein the chromatographic high-pressure sample injection valve has no corrosion phenomenon, and the chromatographic sample injection gas circuit is not blocked.
Example 3
The apparatus shown in fig. 1, wherein,
the storage tank a is a pressure-resistant steel cylinder with the inner diameter of 15cm and the height of 30 cm; the measuring tube b was a transparent pressure-resistant polytetrafluoroethylene tube with a scale having an inner diameter of 1.5cm and a height of 25 cm. The inner diameter ratio of the storage tank a to the measuring pipe b is 15: 1. the upper pipeline and the lower pipeline are communicated between the storage tank a and the measuring pipe b. The support d supports the storage tank a to be vertically placed. The vertical distance of the upper and lower pipelines from the upper and lower ends of the storage tank a, respectively, is 1/15 the height of the storage tank a.
The sampling port is arranged on the side wall of the storage tank a, and the vertical height from the lower end of the storage tank a is 2/7 the height of the storage tank a.
The acid hydrocarbon separator c is a cylindrical container, the ratio of the height to the inner diameter is 1:8, the inner diameter is 20cm, and the height is 2.5 cm; in which glass wool fibers (CR 13-2400. mu.m diameter glass wool fibers from WU lake Baiyun glass fiber Co., Ltd.) were filled. The lower end of the acid hydrocarbon separator c communicates with the sampling port via a sampling line 5 having a diameter of 0.6cm, and the ratio of the cross-sectional area of the acid hydrocarbon separator c to the cross-sectional area of the sampling line 5 is 20: 1.
the device is connected with an alkylation reactor in parallel, and an inlet valve (904L stainless steel valve core) on a feed pipeline is opened to add an alkylation reaction product; the outlet valve (904L stainless steel spool) on the outlet line was opened to allow the alkylation reaction product to fill the apparatus. And closing the inlet valve and the outlet valve, obtaining a sample, separating the device for obtaining the alkylation reaction product from the alkylation reactor, and standing for 8 hours.
The samples in the device are layered, the lower layer is acid liquor, and the upper layer is hydrocarbon. The volume ratio of acid to hydrocarbon in the sample was determined to be 1: 2.
and opening an outlet valve to discharge the acid liquor. The drop in acid hydrocarbon stratification interface was observed through the measurement tube b. And when the layering interface is lower than the sampling port, closing the discharge valve to stop discharging acid. And (4) standing the device, then opening a sampling valve, discharging the hydrocarbon containing the acid gas on the upper layer remained in the storage tank from a sampling port, and entering an acid hydrocarbon separator c through a sampling pipeline. And under the separation action of the coalescence packing, discharging the hydrocarbon sample from which the acid gas is separated out from the sample injection pipeline, measuring the acid content of the hydrocarbon sample, and feeding the hydrocarbon sample into a gas chromatograph for analysis.
The acid content of the hydrocarbon sample was 10 ppm.
And (4) performing multiple times of hydrocarbon sample chromatographic analysis, wherein the chromatographic high-pressure sample injection valve has no corrosion phenomenon, and the chromatographic sample injection gas circuit is not blocked.
The embodiment shows that the device and the method provided by the invention can avoid the corrosion of a chromatographic high-pressure sample injection valve and the blockage of a chromatographic sample injection gas circuit and determine the acid-hydrocarbon ratio of materials in an alkylation reactor.
And when acid discharging operation, acid liquor discharging meets the condition that the layered liquid level is lowered between the sampling port and the lower pipeline, acid-containing liquefied gas does not need to be discharged, and the auxiliary coalescent filler removes the acid-containing liquefied gas, so that the defects of personal injury and environmental pollution caused by splashing of the acid-containing liquefied gas to operating personnel are overcome.
The above drawings describe in detail preferred embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. An acid-to-hydrocarbon ratio analysis and gas chromatography sample injection device for an alkylation reaction product, comprising: a tank (a), a measuring tube (b) with a scale, an acid-hydrocarbon separator (c) filled with a coalescing filler (11), and a holder (d) supporting the tank (a); wherein the content of the first and second substances,
the storage tank (a) and the measuring pipe (b) are vertically arranged in parallel, the upper pipeline (3) is communicated with the upper ends of the storage tank (a) and the measuring pipe (b), and the lower pipeline (4) is communicated with the lower ends of the storage tank (a) and the measuring pipe (b);
the bottom end of the storage tank (a) is communicated with a feeding pipeline (2) with an inlet valve (8), and the top end of the storage tank (a) is communicated with a discharging pipeline (1) with an outlet valve (9); a sampling port (7) with the horizontal height higher than that of the lower pipeline (4) is arranged on the side wall of the storage tank (a);
the acid hydrocarbon separator (c) is communicated with a sampling port (7) through a sampling pipeline (5) with a sampling valve (10), and the coalescence packing (11) is used for separating acid and hydrocarbon in the alkylation reaction product from the storage tank (a); the acid hydrocarbon separator (c) is provided with a sample inlet line (6) for leading out the hydrocarbons separated by the coalescence packing (11).
2. The apparatus of claim 1, wherein the vertical height of the lower line (4) from the lower end of the storage tank (a) is 1/20-1/10 of the height of the storage tank (a); the vertical height of the upper pipeline (3) from the upper end of the storage tank (a) is 1/20-1/10 of the height of the storage tank (a).
3. The device according to claim 1 or 2, wherein the ratio of the inner diameters of the storage tank (a) and the measuring pipe (b) is (10-20): 1.
4. the device according to claim 1, wherein the vertical height of the sampling port (7) from the lower end of the tank (a) is 1/4-1/3 of the height of the tank (a).
5. The apparatus of claim 1, wherein the ratio of the cross-sectional area of the acid-hydrocarbon separator (c) to the cross-sectional area of the sampling line (5) is (1-50): 1.
6. the apparatus of claim 5, wherein the ratio of the cross-sectional area of the acid-hydrocarbon separator (c) to the cross-sectional area of the sampling line (5) is (10-20): 1.
7. the apparatus of claim 1, wherein the acid hydrocarbon separator (c) is a cylindrical vessel, and the ratio of the height to the inner diameter of the acid hydrocarbon separator (c) is 1: (2-20).
8. The apparatus of claim 7, wherein the acid hydrocarbon separator (c) is a cylindrical vessel, and the ratio of the height to the inner diameter of the acid hydrocarbon separator (c) is 1: (5-10).
9. The apparatus of claim 1, wherein the coalescing filler material is selected from at least one of stainless steel mesh, polytetrafluoroethylene ribbon, fiberglass fibers, and polypropylene filaments.
10. A method for acid-to-hydrocarbon ratio analysis and gas chromatography sample injection of an alkylation reaction product, comprising:
(i) removing a sample containing acid and hydrocarbon from an alkylation reactor using the apparatus of any one of claims 1 to 9;
(ii) allowing the apparatus containing the taken sample to stand, and showing delamination of acid and hydrocarbon at the measuring tube (b), and determining the volume ratio of acid and hydrocarbon in the sample from a scale corresponding to the measuring tube (b);
(iii) opening the outlet valve (9) to discharge acid, and closing the outlet valve (9) to stop discharging acid when the layered liquid level in the measuring pipe (b) drops to a position between the sampling port (7) and the lower pipeline (4);
(iv) opening a sampling valve (10), introducing hydrocarbon mixed with a small amount of acid above a sampling port (7) in the device into an acid-hydrocarbon separator (c) through a sampling pipeline (5), separating the acid through a coalescence packing (11), and obtaining the hydrocarbon for gas chromatographic analysis from a sample introduction pipeline (6).
11. The method of claim 10, wherein the act of removing the sample in step (i) comprises: the apparatus is connected in parallel with the alkylation reactor via a discharge line (1) and a feed line (2); opening inlet valve (8) and outlet valve (9) to fill the apparatus with alkylation reaction product containing acid and hydrocarbon in the alkylation reactor; the inlet valve (8) and the outlet valve (9) are closed and separated from the alkylation reactor.
12. An apparatus for the gas chromatography of an alkylation reaction product, comprising a gas chromatograph and a device according to any one of claims 1 to 9, said device communicating with said gas chromatograph via a sample injection line (6).
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