阅读说明：本技术 一种氨乙炔混合气含量的快速检测方法 (A kind of rapid detection method of ammonia acetylene mixing Gas content ) 是由 刘秀金 于 2019-09-06 设计创作，主要内容包括：本发明公开一种氨乙炔混合气含量的快速检测方法。利用常见的廉价化学试剂稀酸、溴化钾的溴饱和溶液、硫化氢检测管和磷化氢检测管,使用简易的针筒注射器,达到快速准确检测氨乙炔混合气的目的。以往采用气相色谱法进行检测,由于样品中含有氨,对气相色谱仪和色谱柱损坏很大,样品检测重现性很差,检测周期长,无法达到实时监控生产。本发明根据氨极易和酸反应得到氨含量,被吸收完氨气的样品主要含有乙炔采用溴法快速检测得到乙炔含量,不凝性气体用减量法计算得到,硫化氢和磷化氢的含量用相应的检测管检测得到。该检测方法具有仪器设备简易、操作简单快速、灵敏度高、试剂廉价易得,节省大量经济与时间成本的优点,生产中推广应用。(The present invention discloses a kind of rapid detection method of ammonia acetylene mixing Gas content.Using common cheap chemical reagent diluted acid, bromine saturated solution, sulfurated hydrogen detection pipe and the hydrogen phosphide detection pipe of potassium bromide, using easy Syringe injector, achieve the purpose that quick and precisely to detect ammonia acetylene gaseous mixture.It was detected in the past using gas chromatography, very big to gas chromatograph and chromatographic column damage due to containing ammonia in sample, sample detection reproducibility is very poor, and detection cycle is long, is unable to reach real time monitoring production.The present invention easily obtains ammonia content with acid reaction according to ammonia, the sample for being absorbed ammonia mainly contains acetylene and is quickly detected using bromine method and obtained acetylene content, incoagulable gas is calculated with Subtraction method, and the content of hydrogen sulfide and hydrogen phosphide detects to obtain with corresponding detection pipe.The detection method have instrument and equipment it is simple, it is easy to operate quickly, high sensitivity, reagent it is cheap and easy to get, the advantages of saving a large amount of economy and time cost, promotes and applies in production.)

1. a kind of rapid detection method of ammonia acetylene mixing Gas content, includes the following steps:

1) using the body of ammonia, acetylene and incoagulable gas in acid solution and the bromine saturated solution of potassium bromide measurement ammonia acetylene gaseous mixture Product content；

2) it is sampled using Teflon FEP gas sampling bag, sampling process sample replaces three times sampler bag, it is ensured that the sample taken Product are representative；It will test with sample gas displacement in syringe gas sampling bag three times with method;

3) in gaseous mixture ammonia level measure: syringe takes volume V (ml) sample, slowly aspiration step 1) in prepare acid solution, Lightly shaking syringe dissolves ammonia sufficiently, and pull syringe is at volume V when liquid level in syringe no longer rises (ml) scale reads the volume V of liquid₁(ml), ammonia volume content X_NH3% are as follows:

X_NH3%=(V-V₁)/V´100%；

4) acetylene and incoagulable gas assay in gaseous mixture: the liquid in step 3) is all given off, by syringe syringe needle It is inserted into the bromine saturated solution of potassium bromide, syringe acetylene is shaken and bromine fast reaction, pull syringe is at the quarter of volume V (ml) Degree reads liquid volume V₂(ml), the volume content X of incoagulable gas_{Incoagulable gas}The volume content X of % and acetylene_C2H2% is respectively as follows:

X_{Incoagulable gas}%=(V-V₂)/V ' 100%,

X_C2H2%=(V₂-V₁)/V´100%；

5) in gaseous mixture hydrogen sulfide and hydrogen phosphide assay: detected with corresponding sulfurated hydrogen detection pipe and hydrogen phosphide detection pipe It obtains.

2. a kind of rapid detection method of ammonia acetylene mixing Gas content according to claim 1, it is characterised in that: the step It is rapid 1) in acid be it is a kind of in sulfuric acid, hydrochloric acid or nitric acid, concentration is 0.5mol/L ~ 2mol/L.

3. a kind of rapid detection method of ammonia acetylene mixing Gas content according to claim 1, it is characterised in that: the step It is rapid ammonia, acetylene and incoagulable gas content 3) to be detected 2) and quickly in a syringe.

4. a kind of rapid detection method of ammonia acetylene mixing Gas content according to claim 1, it is characterised in that: in step 3) ammonia and sour fast reaction are utilized, it may be assumed that

Ammonia is quickly soluble in acid solution, reads liquid volume in syringe, the percentage of liquid volume and samples taken total volume As ammonia volume content.

5. a kind of rapid detection method of ammonia acetylene mixing Gas content according to claim 1, it is characterised in that: in step 4) ammonia in step 3) has been neutralized to the gas of absorption in, has absorbed acetylene with the bromine saturated solution of potassium bromide, it may be assumed that

Acetylene is quickly soluble in the bromine saturated solution of potassium bromide, reads the volume of liquid, and the volume content of incoagulable gas is Subtract the percentage of liquid volume Yu samples taken total volume for population of samples product, the volume content of acetylene is this liquid bulk Product subtracts the percentage of liquid volume and samples taken total volume in step 3).

6. a kind of rapid detection method of ammonia acetylene mixing Gas content according to claim 1, it is characterised in that: in step 5) with sulfurated hydrogen detection pipe and hydrogen phosphide detection pipe detection hydrogen sulfide and Phosphine content in.

7. a kind of rapid detection method of ammonia acetylene mixing Gas content according to claim 1, it is characterised in that: detection institute Bromine saturated solution with reagent acid solution and potassium bromide is reusable, and speed to be absorbed need to be prepared again when declining.

Technical field

The present invention relates to a kind of rapid detection methods of ammonia acetylene mixing Gas content.Specifically to use easy needle Barrel syringe obtains ammonia content according to ammonia and acid reaction, and the sample for being absorbed ammonia mainly contains acetylene and uses bromine method quick Detection obtains acetylene content, and incoagulable gas is calculated with Subtraction method, the corresponding vulcanization of content of hydrogen sulfide and hydrogen phosphide Hydrogen detection pipe and hydrogen phosphide detection pipe detect to obtain, and reach and quick and precisely detect each component volume content in ammonia acetylene gaseous mixture Method.

Background technique

Preparing alkynol as the ethynylation that catalyst carbonylation closes object as solvent alkali metal hydroxide using liquefied ammonia is The reaction of atom economy type, is widely applied in vitamins production at present.As reaction raw material acetylene and ammonia according to one Fixed ratio, which is mixed to form ammonia acetylene gaseous mixture and after special compressor compresses acetylene is dissolved in liquefied ammonia, inputs ethynylation System is reacted.

Ammonia acetylene gaseous mixture mainly contains ammonia, acetylene, hydrogen sulfide, hydrogen phosphide, incoagulable gas nitrogen etc..Ammonia is dissolution second Alkynes solvent；The height of acetylene content not only affects aldehyde ketone ethynylation speed and conversion ratio, and ceases with production safety Correlation, acetylene content is too high to cause system pressure raising security risk big；The content of hydrogen sulfide and hydrogen phosphide affects lower step hydrogen Change the activity and production security of catalyst；Incoagulable gas is nitrogen and micro oxygen, and content is too high to cause system pressure It is big to increase security risk.So the relation with contents of Accurate Determining ammonia acetylene gaseous mixture is to production timeliness and safety.Most texts Report is offered to be detected using gas chromatography, it is strong due to containing ammonia corrosion in sample, gas chromatograph and chromatographic column are damaged Bad very big, sample detection reproducibility is very poor, and detection cycle is long, is unable to reach real time monitoring production, and also some documents are only merely The method of the simple detection acetylene of report, is detected without constituent content each in document report ammonia acetylene gaseous mixture.

The present invention detection method easily obtains ammonia content with acid reaction according to ammonia, and the sample for being absorbed ammonia mainly contains There is acetylene quickly to detect using bromine method and obtain acetylene content, incoagulable gas is calculated with Subtraction method, hydrogen sulfide and hydrogen phosphide Content detect to obtain with corresponding sulfurated hydrogen detection pipe and hydrogen phosphide detection pipe.The detection method have instrument and equipment it is simple, It is easy to operate quickly, high sensitivity, reagent it is cheap and easy to get, the advantages of saving a large amount of economy and time cost, promotes in production and answers With.

Summary of the invention

In order to each constituent content in accurate quickly detection ammonia acetylene gaseous mixture, the object of the present invention is to provide a kind of ammonia The rapid detection method of acetylene mixing Gas content, have instrument and equipment it is simple, it is easy to operate quickly, high sensitivity, reagent it is cheap The advantages of being easy to get, saving a large amount of economy and time cost.

To achieve the goals above, present invention employs following technical solutions:

A kind of rapid detection method of ammonia acetylene mixing Gas content, includes the following steps:

1) prepare the bromine saturated solution of acid solution and potassium bromide (standing one day spare)；

2) it is sampled using Teflon FEP gas sampling bag, sampling process sample replaces three times sampler bag, it is ensured that the sample taken Product are representative；It will test with gas displacement in syringe gas sampling bag three times with method;

3) in gaseous mixture ammonia level measure: syringe takes volume V (ml) sample, slowly aspiration step 1) in prepare acid solution, Lightly shaking syringe dissolves ammonia sufficiently, and pull syringe is at volume V when liquid level in syringe no longer rises (ml) scale reads the volume V of liquid₁(ml), ammonia volume content X_NH3% are as follows:

X_NH3%=(V-V₁)/V´100%；

4) liquid in step 3) all acetylene and incoagulable gas assay in gaseous mixture: gives off to (this process pays attention to Syringe needle not leave liquid level, prevent that gas is carried over or extraneous air enters syringe), by the bromine of syringe syringe needle insertion potassium bromide Saturated solution shakes syringe acetylene and bromine fast reaction, and pull syringe is at the scale of volume V (ml), reads liquid bulk Product V₂(ml), the volume content X of incoagulable gas_{Incoagulable gas}The volume content X of % and acetylene_C2H2% is respectively as follows:

X_{Incoagulable gas}%=(V-V₂)/V ' 100%,

X_C2H2%=(V₂-V₁)/V ' 100%,

Due to hydrogen sulfide and the general source unstripped gas acetylene of hydrogen phosphide, the acetylene for carrying out ethynylation for aldehyde ketone requires hydrogen sulfide For content with hydrogen phosphide at ppm grades, content is very low, ignores in this calculating process；

5) in gaseous mixture hydrogen sulfide and hydrogen phosphide assay: detected with corresponding sulfurated hydrogen detection pipe and hydrogen phosphide detection pipe It obtains.

Above-mentioned steps 1 of the present invention) in acid be it is a kind of in sulfuric acid, hydrochloric acid or nitric acid, concentration is 0.5mol/L ~ 2mol/L.

Above-mentioned steps 2 of the present invention) and 3) quickly detect ammonia, acetylene and incoagulable gas content in a syringe.

In above-mentioned steps 3) utilize ammonia and sour fast reaction, it may be assumed that

Ammonia is quickly soluble in acid solution, reads liquid volume in syringe, the percentage of liquid volume and samples taken total volume As ammonia volume content.

Ammonia in step 3) has been neutralized to the gas of absorption in step 4), has absorbed second with the bromine saturated solution of potassium bromide Alkynes, it may be assumed that

Acetylene is quickly soluble in the bromine saturated solution of potassium bromide, reads the volume of liquid, and the volume content of incoagulable gas is Subtract the percentage of liquid volume Yu samples taken total volume for population of samples product, the volume content of acetylene is this liquid bulk Product subtracts the percentage of liquid volume and samples taken total volume in step 3).

In above-mentioned steps 5) in sulfurated hydrogen detection pipe and hydrogen phosphide detection pipe detection hydrogen sulfide and Phosphine content.

The present invention detects agents useful for same acid solution and the bromine saturated solution of potassium bromide is reusable, speed decline to be absorbed When need to prepare again.

The above-mentioned preferred 100ml of volume V of the present invention.

Advantages of the present invention are as follows: the 1) instrument and equipment that method of the invention uses is simple, as long as can be realized with syringe, keeps away Exempt from using expensive gas chromatograph；

2) the reagent acid solution and potassium bromide-bromine saturated solution and sulfurated hydrogen detection pipe and hydrogen phosphide that method of the invention uses Detection pipe is common cheap reagent；

3) operation is simple for method of the invention, draws certain volume sample successively in acid solution and potassium bromide-using syringe It is dissolved and absorbed in bromine saturated solution, reads liquid volume in syringe respectively, the volume of ammonia, acetylene and incoagulable gas is calculated Content, hydrogen sulfide and Phosphine content directly read to obtain according to the show value of sulfurated hydrogen detection pipe and hydrogen phosphide detection pipe；

4) method of the invention detection speed is fast, and a sample can obtain result as long as less than 10 minutes；

5) method of the invention detection favorable reproducibility, accuracy are high, and ammonia acetylene normal mixture is taken to be measured in parallel 6 times, main group The relative standard deviation RSD of ammonia, acetylene and incoagulable gas assay result is divided to be respectively less than 3.0%.

Specific embodiment

Below with reference to embodiment, the present invention will be further described.