CN87214257U - Device for measuring chloride content in crude oil and oil products - Google Patents
Device for measuring chloride content in crude oil and oil products Download PDFInfo
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- CN87214257U CN87214257U CN 87214257 CN87214257U CN87214257U CN 87214257 U CN87214257 U CN 87214257U CN 87214257 CN87214257 CN 87214257 CN 87214257 U CN87214257 U CN 87214257U CN 87214257 U CN87214257 U CN 87214257U
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- circuit
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- titration cell
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Abstract
The utility model relates to a device for measuring chloride content in crude oil and oil products, which is composed of a microcoulometer and a titration cell. The micro-coulometer uses a zero balance amplifier which is composed of a sampling circuit, a bridge zeroing circuit, a buffer circuit, a V/F converting circuit and display units. The titration cell isolates a cathode compartment from an anode compartment, and also isolates a referential compartment from an anode compartment by using an ion-exchange membrane. The utility model has the advantages of strong anti-interference performance, high stability, convenient operation, wide measuring range and high sensitivity. Electrolyte can be contiguously measured for many times without exchanging.
Description
The utility model belongs to chloride content determining instrument in the Crude Oil ﹠ Petroleum Products.
The general assay method of chloride content can be divided into three kinds in the crude oil: first kind is with the volumetric method of silver nitrate or the total amount of potentiometric determination chlorion; Second kind is to measure the total amount that is converted into villaumite behind sodium, calcium, the magnesium ion content more respectively with flame photometry or atomic absorption spectrophotometry; The third is to measure chloride content by the conductivity of measuring crude oil or the variation of electric current.First method is bigger to low chloride content error at measurment; The used instrument of second method costs an arm and a leg, complicated operation, and also the blank value of being introduced by reagent in the podzolic process of preparation sample is higher, and error at measurment is big; The third method is related with chloride content by means of the change of physical property, and influence factor is also a lot.
Development in recent years microcoulomb analysis faster has fast, accurate, sensitive characteristics, is the better method of measuring Determination of Trace Sulfur, chlorine, nitrogen content.Employed comprehensive Microcoulomb instrument is made up of several parts such as sample introduction, conversion, titration cell and coulomb amplifiers.In the circuit of this comprehensive microcoulomb, measure analog voltage-frequency (V-f) change-over circuit that electric weight adopts digital integrating circuit more or is made up of integrator and Schmidt circuit, the former design is comparatively complicated, and the latter's debugging is difficulty.Because the titration cell volume on this instrument is little, the impedance height, analytic sample must could be measured through chemical conversion, and the price of instrument is more expensive, is difficult to widespread use.And easy microcoulomb analytical equipment also once was used for the muriatic mensuration of aqueous solution, as Jacobsen(Analytical Chemical Acta, Vol.64,280,1973) and Zhou Peishan (" petrochemical complex analytical approach compilation " 143 pages, petroleum industry publishing house, Beijing, nineteen eighty-three) work that the people did such as, but the sensitivity of the Microcoulomb instrument of this simple thermometal indicator electrode is low, can not satisfy the needs that micro-villaumite is measured in the crude oil.
The purpose of this utility model is the deficiency that overcomes in the said method, proposes a kind of highly sensitive, microcoulomb analyser that is used for measuring crude oil and petroleum products chloride content that antijamming capability is strong.
Microcoulomb analyser of the present utility model is to be made of microcoulombmeter and titration cell two parts, its principal character is that microcoulombmeter has adopted the zero balance amplifier of being made up of sample circuit, bridge circuit zeroing, buffer circuit, V-f change-over circuit and display unit, also used electric capacity transition method, sampling and two processes of electrolytic titration are hocketed, separate in time; All to adopt non-water amberplex to isolate between reference chamber and the anode chamber, symmetry was placed about anode that indicator electrode that the composition potential electrode is right and reference electrode and composition electrolysis electrode are right and negative electrode were between amberplex between anode chamber in the titration cell and the cathode chamber.
The work ultimate principle of instrument of the present utility model: the titration cell potential electrode is to exporting a voltage signal to instrument, make comparisons with given signal, when potential electrode equates with given voltage current potential, when direction is identical, amplifier output is zero, and titration cell is in equilibrium state; Sample injects titration cell, and the Cl-in the sample has consumed the Ag in the pond
+, the result makes Ag
+Concentration reduces, and the signal that potential electrode is right changes to some extent, and this difference is delivered to amplifier and amplified, and amplifies the output correspondent voltage and is added in electrolysis electrode to last, and the electrolytic anode electricity bears Ag
+Ag with postreaction consumption
+, measure the Ag of supplement consumed
+Required electric weight can be obtained salt content in the sample according to faraday law again.
Be described in detail architectural feature of the present utility model below in conjunction with accompanying drawing.
Fig. 1 is apparatus structure and principle of work block diagram;
Fig. 2 is the titration cell structural representation;
Fig. 3 is a circuit part circuit block diagram;
Fig. 4 is the wiring diagram of bridge circuit zeroing and buffering circuit;
Fig. 5 is the wiring diagram of V-f change-over circuit.
As shown in Figure 1, at output, four synchronization transistor choppers 6 of input end employing of instrumentation amplifier 2, realize synchro switch, switch arm can be drawn onto solid line and dotted line position.Switch arm is when solid line position, and the potential electrode of titration cell 1 charges to the voltage of primary element to the primary element potential difference (PD) that constitutes to capacitor Co, and stores this electric charge.This moment amplifier 2 ground connection, promptly input signal is zero, amplifier 2 outputs also are zero.When switch arm was in dotted line position, the input voltage of amplifier 2 was gone up the algebraic sum of voltage and given bias voltage bridge circuit 5 given bias voltages by capacitor Co.If this two voltage swing equates that polarity is opposite, then amplifier 2 is input as zero, i.e. △ E=0, and its output also is zero, titration cell 1 is in equilibrium state.After sample injects titration cell 1, chlorion in the sample has consumed the silver ion in the titrant, to cause the variation of indicator electrode current potential, then the voltage on the capacitor Co no longer equals given bias voltage, both difference △ E ≠ 0, and be added to the input end of amplifier 2 through transistor chopper 6, and this signal is one to exchange the ripple signal, C1 is a capacitance.This deviation signal is added on the capacitor C2 by certain polarity after amplifying, and at this moment to be coupled to working electrode right for output voltage, has Faradaic current to flow through titration cell 1 simultaneously, and electricity bears the titrant of silver ion with supplement consumed.Be temporarily stored on capacitor C2 by the right electric weight of electrolysis electrode, in next measuring period, transistor chopper 6 is in solid line position again, the input grounding of amplifier 2, the electric charge that is stored on the capacitor C2 discharges by sample resistance R, the voltage that produces on sample resistance is noted with the form at peak by register 4, and is shown unit 3 integrations and demonstrates electric weight.Electric capacity transition method by above-mentioned makes at electrolysing period, and capacitor C2 stores by the right electric charge of electrolysis electrode, and in the sample period electric charge is all sent, flow through electrolytic cell and sample resistance R, realize that sampling and measuring and two processes of electrolytic titration hocket, and do not take place at one time.Dotted portion is a sample circuit among the figure.
Fig. 2 titration cell is the signal source of titration system.Pond body 13 is columnar glass cylinderes, and two diameters that are fixed with as indicator electrode 11 and reference electrode 10 on the pond lid 12 are 0.8 millimeter filamentary silver.Filamentary silver is immersed in the mixed liquor of acetic acid of solid silver acetate and 70%.The filamentary silver that also is fixed with diameter on the pond lid 12 and is 0.8 millimeter is that 0.5 millimeter platinum filament is as a pair of electrolysis electrode of negative electrode 8 as anode 7 and diameter.The characteristics of titration cell of the present utility model are that electrolytic anode 7 and electrolysis cathode 8, indicator electrode 11 and reference electrode 10 are symmetry placement up and down, use non-water amberplex 15,18 to isolate respectively.Leave injection port 9 to be opened/closed on the pond lid 12, be used for sample injection or change electrolytic solution.A teflon magnetic core stirring rod 16 is arranged in the anode chamber 17, drive stirring by magnetic stirrer during titration, mix to guarantee sample and electrolytic solution.
Potential electrode in the titration cell is compared this changing value then to 10,11 variations that are used for indicating the titration cell concentration of silver ions with the given bias value of Microcoulomb instrument, and with this difference input microcoulomb amplifier 2.Reference electrode 10 of the present utility model is to be inserted in the saturated acetic acid silver electrolyte by filamentary silver to constitute, concentration of silver ions is constant in the reference chamber under certain temperature and pressure, thereby reference electrode 10 current potentials can not change, but the current potential of indicator electrode 11 can change along with the concentration of silver ions of titration cell centre chamber and change.When titration cell is in equilibrium state, potential electrode is to 10,11 current potential just in time equals the given bias voltage 5 of Microcoulomb instrument, but direction is opposite, this moment, the amplifier 2 of Microcoulomb instrument was input as zero, and when the concentration of silver ions in the titration cell reduced, the current potential of potential electrode will change, potential electrode is compared with the given bias voltage 5 of Microcoulomb instrument to 10,11 current potential, and to have produced bias voltage signal be input amplifier 2.
The electrolysis electrode of titration cell is used to produce silver ion to replenish the silver ion that is consumed by chlorion, makes titration cell keep constant concentration of silver ions.Be directly proportional with the output potential size of amplifier 2 owing to flow through the electric current of electrolysis electrode 7,8, therefore measure by the electrolytic anode electricity and give birth to the electric weight that silver ion is consumed, calculate corresponding chlorine (villaumite) content according to the faraday electrolysis law again.
Wiring diagram by the circuit part of Fig. 3 is found out, the tested current i sample resistance R that flows through converts voltage signal V to, behind bridge circuit zeroing circuit 20 and buffering circuit 21, send into V-f change-over circuit 22 again, to counter 7CJ03, become the correspondent frequency signal, having realized i-f conversion (i is an electric current) simply, reliably, is integration ∫ idt(t the time) be transformed into counting with simple circuit.
Concrete wiring diagram by Fig. 4 bridge circuit zeroing circuit 20 and buffering circuit 21 is found out, the voltage signal V on the sample resistance R after R1 and C1 filtering, again behind the bridge circuit of forming via R2～R6, W1, E1, is changed up and down by level and to be used for zeroing.Transistor BG305 and auxiliary element thereof are formed typical 10 times of in-phase amplifiers, on the one hand signal are amplified, and reduce the internal resistance of signal on the other hand, are complementary with realization and V-f change-over circuit 22.
Referring to Fig. 5 V-f change-over circuit.Adopted the DL-8103 thick film circuit to finish the V-f translation function, its output amplitude is 0～8V; Be level shifting circuit with two 3DG6 transistors again, convert the pulse signal of 0～8V the pulse signal of 0～20V to, to satisfy the level needs of counter 7CJ03 counting.
Advantage of the present utility model: because the cathode and anode chamber of titration cell and reference chamber and anode chamber separate with non-water amberplex, thereby reduced impedance, prevented the diffusion of electrolyte, guaranteed the ion migration, improved instrumental sensitivity, the enhancing antijamming capability; Because instrument is highly sensitive, all can provide obvious signal to the chlorion that contains trace in the sample, namely enough about each sample size 1 gram; Use the titration cell of larger capacity (about 145 milliliters of volume), and be to give birth to the silver ion that the silver ion that obtains comes postreaction to consume by the electrolysis electricity, but once add continuous several times working sample behind the electrolyte and the electrolyte that need not more renew, make easy and simple to handle; Owing to adopted zero balance amplifier, use electric capacity transition method, two processes of sampled measurements and electrolytic titration are hocketed, avoided electrical interference; The V-f change-over circuit that the utility model adopts can be realized the i-V conversion simply, reliably, and integration ∫ idt is transformed into counting with simple circuit, thereby reduces the quantity of components and parts, reduces cost, and simplifies the test formality, improves the reliability of instrument.
Claims (4)
1, chloride content analyzer in the Crude Oil ﹠ Petroleum Products, the zero balance amplifier microcoulombmeter of being made up of sample circuit [23], bridge circuit zeroing circuit [20], buffer circuit [21], voltage-frequency conversion (V-f) circuit [22] and display unit [3] is constituted of the present utility model being characterised in that with the potential electrode that is made of reference electrode [10] and indicator electrode [11] respectively to the electrolysis electrode that reaches positive and negative electrode [7], [8] formation to the micro-coulometric titration pond of forming:
(1) sample circuit [23] reaches with amplifier [2] respectively and by the titration cell potential electrode [10], [11] is connected with titration cell [1];
(2) bridge circuit zeroing circuit [20] is connected with sample circuit [23] and buffer circuit [21] respectively;
(3) buffer circuit [21] is connected with bridge circuit zeroing circuit [20] and V-f change-over circuit [22] respectively;
(4) V-f change-over circuit [22] is connected with display unit [3] and register [4] respectively;
(5) potential electrode that on the Chi Gai [12] of titration cell, is fixed with the indicator electrode [11] that makes with filamentary silver and reference electrode [10] to and the electrolysis electrode of the anode [7] that makes by filamentary silver respectively and the negative electrode [8] that makes by platinum filament right, reference electrode [10] is immersed in the mixed liquor of solid silver acetate and 70% water acetic acid.
2, analyzer according to claim 1 is characterized in that output, the input end of amplifier (2) adopts synchronization transistor chopper (6) to realize synchro switch.
3, analyzer according to claim 1 is characterized in that 10 times of in-phase amplifiers that the preceding employing of V-f change-over circuit (22) is made up of transistor and auxiliary element are complementary with it, adopt the DL-8103 thick film circuit to finish the V-f translation function simultaneously.
4, analyzer according to claim 1, it is characterized in that between titration cell reference chamber (14) and anode chamber (17), all adopt non-water amberplex (15), (18) to isolate between cathode chamber (19) and anode chamber (17), electrolysis cathode (8) and anode (7) and reference electrode (10) and indicator electrode (11) all are in laterally zygomorphic position respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87214257 CN87214257U (en) | 1987-10-16 | 1987-10-16 | Device for measuring chloride content in crude oil and oil products |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87214257 CN87214257U (en) | 1987-10-16 | 1987-10-16 | Device for measuring chloride content in crude oil and oil products |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN87214257U true CN87214257U (en) | 1988-07-06 |
Family
ID=4828617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87214257 Withdrawn CN87214257U (en) | 1987-10-16 | 1987-10-16 | Device for measuring chloride content in crude oil and oil products |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN87214257U (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100401055C (en) * | 2004-07-29 | 2008-07-09 | 宝山钢铁股份有限公司 | Method for measuring total content of chlorine in iron ore and brown iron oxide |
| CN104865306A (en) * | 2015-04-23 | 2015-08-26 | 中国制浆造纸研究院 | Detection method of adsorbable organic chlorides in solid sample |
| CN108693073A (en) * | 2018-04-08 | 2018-10-23 | 东营联合石化有限责任公司 | A kind of residual oil salt content assay method |
| CN108982750A (en) * | 2018-07-09 | 2018-12-11 | 湖州吉昌化学有限公司 | The detection method of chlorinity in a kind of 2- ethyl hydrazine |
-
1987
- 1987-10-16 CN CN 87214257 patent/CN87214257U/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100401055C (en) * | 2004-07-29 | 2008-07-09 | 宝山钢铁股份有限公司 | Method for measuring total content of chlorine in iron ore and brown iron oxide |
| CN104865306A (en) * | 2015-04-23 | 2015-08-26 | 中国制浆造纸研究院 | Detection method of adsorbable organic chlorides in solid sample |
| CN108693073A (en) * | 2018-04-08 | 2018-10-23 | 东营联合石化有限责任公司 | A kind of residual oil salt content assay method |
| CN108982750A (en) * | 2018-07-09 | 2018-12-11 | 湖州吉昌化学有限公司 | The detection method of chlorinity in a kind of 2- ethyl hydrazine |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| RN01 | Renewal of patent term | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |