CN104128167A - Preparation method of gas chromatographic column filler for hydrogen isotope quantitative analysis and manufacture process of gas chromatographic column - Google Patents

Abstract

The invention discloses a preparation method of a gas chromatographic column filler for hydrogen isotope quantitative analysis and a manufacture process of a gas chromatographic column. The preparation method of the filler comprises the steps: S1, placing a 4A molecular sieve in an FeCl3 solution, and soaking; S2, allowing the 4A molecular sieve to adsorb FeCl3, Fe(OH)3 and a hydrate of Fe(OH)3 until being saturated, and then filtering to remove the FeCl3 solution; S3, putting the 4A molecular sieve into distilled water, heating to boil, fully hydrolyzing FeCl3 to generate Fe(OH)3 and the hydrate thereof, and tightly adsorbing on the 4A molecular sieve; S4, filtering to remove the distilled water, baking the 4A molecular sieve, and dehydrating Fe(OH)3 and the hydrate thereof to produce Fe2O3; and S5, cooling the 4A molecular sieve to the room temperature, and passivating with CO2. The filler has good separation effect on hydrogen isotopes, is suitable for manufacturing the gas chromatographic column with large load amount, thereby having quite high application values.

Description

The preparation method of gas-chromatography column packing that hydrogen isotope quantitative analysis is used and the manufacture craft of chromatographic column thereof

Technical field

The present invention relates to a kind of gas chromatographic column, what be specifically related to is the preparation method of gas-chromatography column packing and the manufacture craft of chromatographic column thereof that a kind of hydrogen isotope quantitative analysis is used.

Background technology

The increasingly serious energy crisis of the mankind has been impelled the formal startup of international thermonuclear fusion reactor (ITER) plan, discharges greatly, pollutes little nuclear fusion energy exploitation also start to get most of the attention for energy.The production of fusion reactor fuel and processing are one of fusion reactor core technologies, and this reclaims, recycles with tritium propagation covering (TBM) and produce in real time tritium (to supplement the consumption of tritium) comprising the deuterium tritium in plasma ash discharge.No matter be fuel recycle process or tritium propagation leaching process, all need the technology of the quick or even on-line measurement of using hydrogen isotope.

Hydrogen isotope has identical chemical property substantially, so can only utilize the minute differences of its physical property to realize to their analysis.At present, hydrogen isotope analysis method mainly contains mass spectrography, Raman spectroscopy, gas chromatography.The whole bag of tricks has its limitation, and as the effect of high energy electron in mass spectrography can be accelerated the disproportionated reaction of hydrogen isotope gas molecule, and equipment volume is large, expensive; Laser Raman spectroscopy cannot be analyzed inert gas, and in the time there is impurity element in sample gas, can produce interference; The analytical cycle of gas chromatography is longer, and in general error is also larger.

Although there is certain defect, gas chromatography has its important advantage: instrument low price, Operation and Maintenance are simple.If can amass, shorten analytical cycle, improve precision and the accuracy analyzed by reduction printer body, will become the comparatively desirable instrument in hydrogen isotope analysis aspect.

Hydrogen isotope protium (H), deuterium (D), tritium (T) mutually combine and can form same core hydrogen H ₂, D ₂, T ₂with heteronuclear hydrogen HD, HT, DT.In same core hydrogen, due to nuclear spin state difference, just there iing again dividing of (ortho) secondary (para), and in the time containing tritium in sample, also having the decay constant of tritium ³he, not only changes because of the decay of tritium containing the composition of tritium gas meanwhile, is also accompanied by the secondary species that radiation-actuate produces.Therefore, separates for eliminate positive parahydrogen in the time separating hydrogen isotope gas the hydrogen peak division causing, generally choose and align parahydrogen conversion and have the paramagnetic material of catalytic action to apply modification to chromatographic stationary phases.

At present, about the coating modification of chromatographic stationary phases, someone has adopted the V that coating quality mark is 5% ₂o ₄the 4A molecular sieve chromatography post of (vanadium dioxide) and applied 5% Fe ₂o ₃4A molecular sieve chromatography post, then at-196 DEG C, separated respectively HT and T ₂.But, utilize V ₂o ₄the 4A molecular sieve chromatography column method applying, due to the stable colloidal solution of the water-soluble easy formation of barium oxide, thereby has caused the efficiency of coating lower; In addition, although+vanadium of 4 valencys has paramagnetism, raw material V ₂o ₅easily be reduced into various low oxide, make applicator V ₂o ₄in to contain other valence state impurity many, affected applicator and aligned the catalytic action of parahydrogen conversion.And employing Fe ₂o ₃in the 4A molecular sieve chromatography column method applying, because the ammoniacal liquor passing into can make Fe ₂o ₃fast hydrolyzing forms flocculent deposit, thereby easily causes coating inhomogeneous, has affected the effect that applies modification, has then also affected the separating effect of hydrogen isotope.

The people such as the applicant's employee Wang Xiaoying, Qin Cheng also have the γ-Al that participates in designing a kind of modification ₂o ₃chromatographic column, this kind of chromatographic column is stronger to the reserve capability of hydrogen isotope, is applicable to making the little capillary column of load capacity.But this technical scheme, because the symmetry at peak is good not, is easily trailed, and contamination resistance a little less than, thereby be not suitable for making the chromatographic column that load capacity is larger.And along with the progressively development of science and technology, making heavy load amount and the strong chromatographic column of contamination resistance has become a kind of inevitable trend, therefore, be necessary chromatographic column to improve.

Summary of the invention

For above-mentioned technical deficiency, the invention provides the preparation method of gas-chromatography column packing and the manufacture craft of chromatographic column thereof that a kind of hydrogen isotope quantitative analysis is used, it has the effective and applicable feature of making the chromatographic column that load capacity is larger of hydrogen isotope separation.

To achieve these goals, the technical solution used in the present invention is as follows:

The preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis is used, comprises the following steps:

S1: 4A molecular sieve is placed in to FeCl ₃in solution, soak this FeCl ₃and by part FeCl ₃the Fe (OH) that hydrolysis generates ₃and Fe (OH) ₃hydrate be all adsorbed on 4A molecular sieve; The order number of described 4A molecular sieve is 80～100 orders;

S2:4A molecular sieve adsorption FeCl ₃, Fe (OH) ₃and Fe (OH) ₃hydrate until saturated, then filtering FeCl ₃solution;

S3: absorption is had to FeCl ₃and Fe (OH) ₃and the 4A molecular sieve of hydrate puts in distilled water heating and boil, make FeCl ₃complete hydrolysis generates Fe (OH) ₃and hydrate adsorbed close are on 4A molecular sieve, adsorb unstable FeCl simultaneously ₃, Fe (OH) ₃and Fe (OH) ₃hydrate detach 4A molecular sieve;

S4: filter distilled water, and 4A molecular sieve is toasted, make the Fe (OH) on it ₃and hydrate dehydration generates Fe ₂o ₃;

S5: 4A molecular sieve is cooled to room temperature, and uses CO ₂passivation, obtains filler.

Specifically, in described step S1, take 2～8 grams of 4A molecular sieves and be placed in FeCl ₃in solution, soak.

Further, in described step S1,4A molecular sieve is placed in to the FeCl of 200～300ml ₃in solution, soak 2～6h.

As preferably, in described step S1, FeCl ₃solution is saturated solution.

Again further, in described step S3,4A molecular sieve is put into 200～600ml distilled water and boil.

Further, in described step S4,4A molecular sieve is put in baking oven and toasted, the temperature and time of baking is respectively 100～300 DEG C and 6～10h.

Further, in described step S5, by 4A molecular sieve CO ₂passivation 4～8h.

On the basis of above-mentioned filler, the present invention is based under same inventive concept, three kinds of techniques of utilizing above-mentioned filler to make chromatographic column are also provided, as described below:

Technique one

Comprise the following steps:

S1: filler is filled in stainless steel tube, and vibrations are tamped;

S2: utilize CO ₂mode with 3～5ml/min is carried out purge to stainless steel tube, and the purge time is 2～4h, then stainless steel tube is exposed in air more than 30 days;

S3: utilize pure Ne gas, in the mode of 8～5ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days, obtains chromatographic column.

Technique two

Comprise the following steps:

S1: filler is filled in stainless steel tube, and vibrations are tamped;

S2: utilize CO ₂mode with 3～5ml/min is carried out purge to stainless steel tube, and the purge time is 2～4h, then stainless steel tube is exposed in air more than 30 days;

S3: utilize pure Ne gas, in the mode of 8～10ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days;

S4: passing under the condition of pure Ne gas, stainless steel tube is heated to 200～300 DEG C, and maintains 3～5h;

S5: stainless steel tube temperature is down to room temperature, and uses by the Ne gas of water-vapo(u)r saturation, in the mode of 25～30ml/min, stainless steel tube is carried out to purge passivation 100～120h, obtain chromatographic column.

Technique three

Comprise the following steps:

S1: filler is filled in stainless steel tube, and vibrations are tamped;

S2: utilize CO ₂mode with 3～5ml/min is carried out purge to stainless steel tube, and the purge time is 2～4h, then stainless steel tube is exposed in air more than 30 days;

S3: utilize pure Ne gas, in the mode of 8～10ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days;

S4: passing under the condition of pure Ne gas, stainless steel tube is heated to 200～300 DEG C, and maintains 3～5h;

S5: stainless steel tube temperature is down to room temperature, and uses by the Ne gas of water-vapo(u)r saturation, in the mode of 25～30ml/min, stainless steel tube is carried out to purge passivation 100～120h;

S6: under the condition below 150 DEG C, by stainless steel tube heating 1～1.5h, and adopt pure Ne gas to carry out purge to stainless steel tube, repeat this step 1～3 time, obtain chromatographic column.

Compared with prior art, the present invention has following beneficial effect:

(1) the present invention adopts FeCl ₃the mode that solution soaks 4A molecular sieve and boils with distilled water, makes FeCl ₃the Fe (OH) that solution complete hydrolysis generates ₃and hydrate adsorbed close is in the sieve aperture of 4A molecular sieve, then 4A molecular sieve is toasted, and obtains being coated with Fe ₂o ₃4A molecular sieve, finally re-use CO ₂4A molecular sieve is carried out to passivation, can obtain the chromatographic column filler of excellent performance.The present invention has used FeCl dexterously ₃the mode of solution hydrolysis, absorption makes Fe (OH) ₃and hydrate is coated on 4A molecular sieve, first soak, then adding distil water boils, and then baking dehydration generates Fe ₂o ₃, at present, this technological means is still belonging to pioneering aspect application gas chromatography separation hydrogen isotope.And thus, not only take full advantage of FeCl ₃the characteristic of solution, makes the Fe of its hydrolysis ₂o ₃be adsorbed in well on 4A molecular sieve, and make Fe by the mode of soaking, distilled water boils ₂o ₃absorption is firm, thereby has avoided Fe ₂o ₃affect the uniform effect of coating because being easily hydrolyzed formation flocculent deposit, therefore, compare the existing ammoniacal liquor that passes into and form Fe ₂o ₃technical scheme, the scheme of the present invention design has solved Fe well ₂o ₃apply inhomogeneous problem, significantly improved the performance of chromatographic column, make its separating effect to hydrogen isotope better.

(2) the present invention adopts CO ₂4A molecular sieve is carried out to passivation, due to CO ₂be strong nonpolar molecule, and 4A molecular sieve is evenly coated with Fe ₂o ₃, therefore, CO ₂passivation can make the adsorption activity of the each adsorption potential in 4A molecular sieve surface close, and the range of linearity of adsorption isotherm is wider, and hydrogen deuterium isotope is had to appropriate adsorption capacity.Chromatographic column prepared by the present invention, its separating degree reduces degree compared with γ-Al ₂o ₃gently, can obtain very symmetrical chromatographic peak, and the contamination resistance of chromatographic column and bearing capacity very strong, therefore, the filler of the present invention design is very applicable to making the chromatographic column of heavy load amount.

(3) the present invention, making in the technique of chromatographic column, except the feature of filler self, has also adopted CO ₂with pure Ne inert gas and by the mode that changes temperature, the stainless steel tube of having loaded filler is carried out repeatedly to purge and passivation, thereby can form the chromatographic column of the multiple different states of activation, and then can select flexibly the chromatographic column of the different states of activation to separate hydrogen isotope according to actual conditions, its applicability is very strong, has good versatility.

(4) reasonable idea of the present invention, designs ingeniously, and preparative chromatography column packing process is simple, does not need to add any precipitating reagent, PH conditioning agent etc., therefore, with low cost, efficiency is high, and the lock out operation for hydrogen isotope is easy, and analytical cycle is short, and analysis result accuracy is high.

(5) the present invention is by being engaged in art technology senior engineer's design and development for many years, its technical scheme has very strong specific aim, and break through the restriction of prior art, realize great innovation, meet development in science and technology trend, therefore, the present invention compared with prior art, there is outstanding substantive distinguishing features and significant progressive, be suitable for large-scale promotion application.

Brief description of the drawings

Fig. 1 is the preparation flow schematic diagram of chromatographic column filler of the present invention.

Fig. 2 is the relative retention value r of the each component of hydrogen isotope in the different state of activation chromatographic columns of the present invention-embodiment _i,sand the lnr between reduced mass μ _i,s-ln μ graph of a relation.

Fig. 3 is the adjustment retention time t ' that the different column caps of A chromatographic column of the present invention-embodiment making are depressed the each component of hydrogen isotope _rand the lnt ' between reduced mass μ _r-ln μ graph of a relation.

Fig. 4 is the adjustment retention time t ' that the different column caps of E chromatographic column of the present invention-embodiment making are depressed the each component of hydrogen isotope _rand the lnt ' between reduced mass μ _r-ln μ graph of a relation.

When Fig. 5 is 200KPa column cap pressure, the adjustment retention time t ' of the each component of hydrogen isotope in the different state of activation chromatographic columns of the present invention-embodiment _rand the lnt ' between reduced mass μ _r-ln μ graph of a relation.

When Fig. 6 is 200KPa column cap pressure, the present invention-embodiment chromatographic column lnt ' _rgraph of a relation between slope a ' and the intercept b ' of-ln μ fitting a straight line.

Fig. 7 is the present invention-embodiment mean linear velocity of carrier gas degree time, column length L, mean linear velocity of carrier gas degree the adjustment retention time t ' of chromatographic column state of activation parameter a ' and the each component of hydrogen isotope _rbetween graph of a relation.

Detailed description of the invention

Below in conjunction with drawings and Examples, the invention will be further described, and embodiments of the present invention include but not limited to the following example.

Embodiment

The present invention is mainly used in gas chromatographic column aspect, and it provides the preparation technology of gas-chromatography column packing, and the chromatographic column of utilizing filler that this preparation technology obtains to make, and as shown in Figure 1, the technological process of preparing gas-chromatography column packing of the present invention is as follows:

(1) taking 2～8 grams and order number is 80～100 object 4A molecular sieves, and is placed in the FeCl of 200～300ml ₃in solution, soak 2～6h, part FeCl ₃be hydrolyzed into Fe (OH) ₃and Fe (OH) ₃hydrate; The order number of described 4A molecular sieve is 80～100 orders;

(2) FeCl ₃the Fe (OH) that hydrolysis generates ₃and Fe (OH) ₃hydrate, and a large amount of unhydrolysed FeCl ₃all be adsorbed in the sieve aperture of 4A molecular sieve, until 4A molecular sieve reaches capacity, then filtering FeCl ₃solution; The present invention can adopt saturated or undersaturated FeCl ₃solution soaks 4A molecular sieve, and difference is only, saturated FeCl ₃solution can further be accelerated the adsorption rate of 4A molecular sieve, shortens the time of absorption;

(3) absorption is had to FeCl ₃, Fe (OH) ₃and Fe (OH) ₃the 4A molecular sieve of hydrate is put in the distilled water of 200～600ml and is heated and boil, in the process of boiling, and FeCl ₃complete hydrolysis generates Fe (OH) ₃and hydrate adsorbed close be on 4A molecular sieve, some adsorb unstable FeCl simultaneously ₃, Fe (OH) ₃and Fe (OH) ₃hydrate can detach 4A molecular sieve;

(4) filter distilled water, and 4A molecular sieve is put into internal temperature is that the baking oven of 100～300 DEG C toasts 6～10h, makes the Fe (OH) on 4A molecular sieve ₃and hydrate dehydration generates Fe ₂o ₃, molecular sieve is activated;

(5) 4A molecular sieve is cooled to room temperature, and uses CO ₂passivation 4～8h, obtains filler.

Prepare after filler, the present embodiment adopts three sets of plan to make the chromatographic column of five kinds of different states of activation, and these five kinds of chromatographic columns can contain the applicable cases of current gas chromatography aspect hydrogen isotope separation substantially.

The present embodiment is made the chromatographic column that obtains structurally by the stainless steel tube of external diameter 1.6mm, internal diameter 0.78mm, length 4.5m, and the connector that is connected to these stainless steel tube two ends forms.

The production program of the chromatographic column of five kinds of different states of activation is as follows respectively:

State one

(1) filler is filled in stainless steel tube, and vibrations are tamped;

(2) utilize CO ₂mode with 3～5ml/min is carried out purge to stainless steel tube, and the purge time is 2～4h, then stainless steel tube is exposed in air more than 30 days;

(3) utilize pure Ne gas, in the mode of 8～10ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days, obtains the chromatographic column of the state of activation one.

State two

On the basis of state one, pass into pure Ne gas, and stainless steel tube is heated to 200～300 DEG C, and maintain 3～5h.Finally stainless steel tube temperature is down to room temperature, and uses by the Ne gas of water-vapo(u)r saturation, in the mode of 25～30ml/min, stainless steel tube is carried out to purge passivation 100～120h, obtain the chromatographic column of the state of activation two.

State three

On the basis of state two, under the condition below 100 DEG C, by stainless steel tube heating 1～1.5h, and adopt pure Ne gas to carry out purge to stainless steel tube, obtain the chromatographic column of the state of activation three.

State four

On the basis of state three, again, under the condition below 100 DEG C, by stainless steel tube heating 1～1.5h, and adopt pure Ne gas to carry out purge to stainless steel tube, obtain the chromatographic column of the state of activation four.

State five

On the basis of state four, under the condition below 150 DEG C, by stainless steel tube heating 1～1.5h, and adopt pure Ne gas to carry out purge to stainless steel tube, obtain the chromatographic column of the state of activation five.

On the chromatographic column basis of above-mentioned filler preparation and making, the present embodiment is set forth technical scheme of the present invention and technique effect with a test case.

Take 2 gram of 100 object 4A molecular sieve, be placed in the FeCl of 200ml ₃in saturated solution, soak 4h, after 4A molecular sieve adsorption is saturated, filter FeCl ₃saturated solution.Then, add the distilled water of 400ml to boil, treat the FeCl in 4A molecular sieve sieve aperture ₃and Fe (OH) ₃and after hydrate absorption firmly, filter distilled water.

The 4A molecular sieve that filters distilled water is put in the baking oven of 200 DEG C and toasted 8h, be then cooled to room temperature, finally utilize CO ₂passivation 4h, obtains filler.

The filler that utilization obtains, adopts technique of the present invention to produce respectively five kinds of chromatographic column A, B, C, D, E, as follows:

A: filler is filled in stainless steel tube, and vibrations tamp, then utilize CO ₂mode with 5ml/min is carried out purge to stainless steel tube, and the purge time is 4h, then stainless steel tube is exposed in air to 30 days, exposes 30 days the above object and is to make the further passivation of 4A molecular sieve in stainless steel tube.Finally, utilize pure Ne gas, in the mode of 10ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days, can obtain A chromatographic column.

B: on A basis, utilize pure Ne gas, in the mode of 10ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days, then passes into pure Ne gas, and stainless steel tube is heated to 300 DEG C, maintains 5h.Finally, stainless steel tube temperature is down to room temperature, and uses by the Ne gas of water-vapo(u)r saturation, in the mode of 25/min, stainless steel tube is carried out to purge passivation 100h, obtain B chromatographic column.

C: on B basis, under the condition below 100 DEG C, stainless steel tube is heated to 1h, and adopt pure Ne gas to carry out purge to stainless steel tube, obtain C chromatographic column.

D: on C basis, again, under the condition below 100 DEG C, stainless steel tube is heated to 1h, and adopt pure Ne gas to carry out purge to stainless steel tube, obtain D chromatographic column.

E: on D basis, under the condition below 150 DEG C, stainless steel tube is heated to 1h, and adopt pure Ne gas to carry out purge to stainless steel tube, obtain E chromatographic column.

What deserves to be explained is, the above-mentioned test case parameter used of preparing filler and chromatographic column of the present invention is only preferably parameter of some of them, other parameters that the present invention records are when for the preparation of filler and chromatographic column, filler and chromatographic column prepared by the preparation that obtained separately and result of use and this test case are more or less the same, therefore the present embodiment will not enumerate other cases.

Obtain, after five kinds of chromatographic columns, it being linked in chromatograph by connector separately according to above-mentioned test case, then carry out the test of protium deuterium mist discrete testing.The parameter of test is respectively 23 DEG C of temperature, pressure 94KPa, chromatographic column temperature 77K; Chromatogram carrier gas is Ne gas.The column cap of chromatographic column is pressed the post tail volume flow rate (F of (Pi) and chromatogram carrier gas ₀) the available formula of relation (1) represent:

lnF _o＝1.50461lnP _i-5.26273 (1)

In formula:

F _o---carrier gas Ne is at the volume flow rate (ml/min) in post tail exit;

P _i---column cap is pressed (KPa).

Test has been prepared and has been included He (10%), H ₂(45%), D ₂(45%) gaseous mixture, and the H that under room temperature, the H:D ratio of catalytic equilibration is 1:1 ₂, HD, D ₂the gases such as gaseous mixture are as sample gas, and chromatographic column is soaked in liquid nitrogen.

With ⁴he or ³the retention time of He is dead time t _mcalculate the adjustment retention time t' of each component _r, with D ₂adjustment retention time be benchmark, calculate the relative retention value r of each gas component _i,s, taking the test of A, E chromatographic column as example, in two tests, adjustment retention time and the relative retention value of each gas component are shown in table 1 below, the reduced mass μ of hydrogen isotope gas is as shown in table 2.

Table 1

Isotope gas	H 2	HD	HT	D 2	DT	T 2
							Reduced mass μ	0.5039	0.6717	0.7554	1.0071	1.2076	1.5080

Table 2

From table 1, in the chromatographic column situation of the same state of activation, when column cap is pressed difference, the adjustment retention time t ' of the each component of hydrogen isotope _ralthough different, relative retention value r _i,sbut be consistent, r _i,sreflected the relative reserve capability of hydrogen isotope gas in chromatographic column, the filling kind and the state of activation that only use with chromatographic column are relevant.

In table 1, also list the relative retention value r of hydrogen isotope gas under the different states of activation _i,s.According to the data of table 1, obtain lnr _i,s-ln μ graph of a relation (Fig. 2), can know thus, under the different state of activation of chromatographic column, and lnr _i,sall linear with ln μ, available formula (2) represents:

lnr _i,s＝a′lnμ+b (2)

In formula:

A '---lnr _i,sthe slope of-ln μ fitting a straight line;

B---lnr _i,sthe intercept of-ln μ fitting a straight line.

Because intercept b can draw according to the coordinate of graph of a relation, therefore, according to above-mentioned formula, just can obtain the data of a ' in five kinds of chromatographic column A, B, C, D, E, as shown in table 3:

The state of activation	A	B	C	D	E
						a′	0.51817	0.40295	0.48524	0.54143	0.66876

Table 3

Draw nt ' according to the data in table 1 again _r-ln μ graph of a relation, and equally taking the test of A, E chromatographic column as example, known, the same state of activation, different column cap are depressed, lnt ' _rwith also linear (Fig. 3,4) of ln μ, available formula (3) represents:

lnt′ _R＝a′lnμ+b′ (3)

In formula:

A '---lnt ' _rthe slope of-ln μ fitting a straight line;

B '---lnt ' _rthe intercept of-ln μ fitting a straight line.

Equally, the value of b ' can draw according to the coordinate of graph of a relation, and therefore, according to above-mentioned formula, the value that can obtain a ', b ' in five kinds of chromatographic column A, B, C, D, E is as shown in table 4:

Table 4

Can be found out by table 3,4, under the same state of activation of chromatographic column, the slope value in formula (2), (3) is identical, shows that slope value is only relevant with the state of activation of chromatographic column.And as can be seen from Table 4, b ' presses (or flow rate of carrier gas) relevant with the state of activation and the column cap of chromatographic column.

With P _i=200KPa is example, then with the data in table 4, and formula (3), calculates the lnt ' of all the other B, C, tri-kinds of chromatographic columns of D _r-ln μ graph of a relation (Fig. 5), five kinds of chromatographic column lnt ' _rslope and the intercept of-ln μ fitting a straight line are as shown in table 5:

The state of activation	A	B	C	D	E
						a′	0.52287	0.40295	0.48524	0.54143	0.64973
b′	1.44670	0.96732	1.31502	1.52368	1.99102

Table 5

Utilize the data of this table 5, simulate the linear graph (Fig. 6) of a ' and b ', its relation is as shown in formula (4):

b′＝4.12803a′-0.69968 (4)

Can obtain formula (5) by formula (3):

t′ _R＝e ^b′μ ^a′ (5)

Therefore, can show that by formula (4), (5) column cap is pressed in t ' under 200KPa _rrelational expression (6) with reduced mass μ and a ':

t′ _R＝e ^{4.12803a′-0.69968}μ ^a′ (6)

Suppose that the mean linear velocity of carrier gas that 200KPa column cap is depressed is because the length of chromatographic column is 4.5m, therefore, according to the fundamental relation between chromatogram component net retention volume and fixing phase loadings and flow rate of carrier gas, can derive t ' _rwith column length L, mean linear velocity of carrier gas degree relation between chromatographic column state of activation parameter a ', as shown in Fig. 7 and formula (7):

$t_R^{\′}=\frac{L}{4.5}\×\frac{{\stackrel{\‾}{u}}^{\′\′}}{\stackrel{\‾}{u}}{e}^{4.12803a^{\′}-0.69968}{\mathrm{\μ}}^{a^{\′}}---\left(7\right)$

In formula:

L---column length, m;

---mean linear velocity of carrier gas degree, cms ^-1.

Merge, simplify constant term, can obtain more general relational expression (8):

$t_R^{\′}=\frac{L}{\stackrel{\‾}{u}}{e}^{c_1{a}^{\′}-c_2}{\mathrm{\μ}}^{a^{\′}}---\left(8\right)$

In formula:

C ₁, c ₂---constant, relevant with kind and the phase ratio β of fixing phase.

With D ₂peak is example, and the column cap being obtained by experimental result is pressed while being 200KPa, the high H of actual plate of the chromatographic column of the different states of activation _effas shown in table 6:

Table 6

And under E chromatographic column, D when different column caps are pressed ₂the high H of actual plate at peak _effas shown in table 7:

Column cap is pressed P i(KPa)	500	400	300	200
					D 2H eff(mm)	2.986	2.268	1.779	1.347

Table 7

As can be seen from Table 6, chromatographic column is to the high H of the actual plate of hydrogen isotope gas _effunder different state of activation chromatographic columns, substantially do not change (under the different states of activation, the speed that hydrogen isotope gas is set up adsorption-desorption balance at fixing phase surface is close), can be found out H by table 7 _effalong with the increase of column cap pressure (or flow rate of carrier gas) increases.

Press situation when 400KPa as example taking column cap again, the high H of the actual plate of hydrogen isotope gas _effas shown in table 8:

Table 8

As can be seen from Table 8, except H ₂outward, H _effincrease along with the increase of isotope gas molecular weight, this with the resistance to mass tranfer of isotope gas molecule in mobile phase be inversely proportional to coefficient of molecular diffusion relevant, and H ₂peak is actually ortho-hydrogen (o-H ₂) and parahydrogen (p-H ₂) the fusion peak at peak, therefore H ₂peak wider, and H _effhigher.

Again taking B, E chromatographic column as example, its T ₂chromatographic peak tailing factor is as shown in table 9:

Table 9

As can be seen from Table 9, the chromatographic column after the passivation of pure Ne gas, the symmetry at its peak is better, and sample size increases less on the impact of peak symmetry (or post effect), and the bearing capacity of sample is stronger.

In hydrogen isotope gas, select the moderate D of separating difficulty ₂with DT be representative, in chromatogram, the definition of separating degree R is as shown in formula (9):

$R=\frac{2(t_{R\left(\mathrm{DT}\right)}^{\′}-t_{R\left(D_2\right)}^{\′})}{W_{D_2}+W_{\mathrm{DT}}}---\left(9\right)$

In formula:

W _d2, W _dT---D ₂, the peak width of DT, min.

Can obtain:

$R=\frac{\sqrt{L}(t_{R\left(\mathrm{DT}\right)}^{\′}-t_{R\left(D_2\right)}^{\′})}{2(t_{R\left(D_2\right)}^{\′}\sqrt{H_{\mathrm{eff}\left(D_2\right)}}+t_{R\left(\mathrm{DT}\right)}^{\′}\sqrt{H_{\mathrm{eff}\left(\mathrm{DT}\right)}})}---\left(10\right)$

Calculating required column length L when reaching particular separation and spending according to formula (8) and formula (10) is:

$L=\frac{{4R}^2{(\sqrt{H_{\mathrm{eff}\left(D_2\right)}}{t}_{R\left(D_2\right)}^{\′}+\sqrt{H_{\mathrm{eff}\left(\mathrm{DT}\right)}}{t}_{R\left(\mathrm{DT}\right)}^{\′})}^2}{{(t_{R\left(\mathrm{DT}\right)}^{\′}-t_{R\left(D_2\right)}^{\′})}^2}=\frac{{4R}^2{(\sqrt{H_{\mathrm{eff}\left(D_2\right)}}{\mathrm{\μ}}_{D_2}^{a^{\′}}+\sqrt{H_{\mathrm{eff}\left(\mathrm{DT}\right)}}{\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}})}^2}{{({\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}}-{\mathrm{\μ}}_{D_2}^{a^{\′}})}^2}---\left(11\right)$

Visible, reach the required column length L of particular separation degree relevant with state of activation a ' with post effect.

The certain chromatographic column of filling state has within the scope of certain flow rate:

$H_{\mathrm{eff}}=k\stackrel{\‾}{u}---\left(12\right)$

In formula:

K---proportionality coefficient.

:

$L=\frac{4\stackrel{\‾}{u}{R}^2{(\sqrt{k_{D_2}}{\mathrm{\μ}}_{D_2}^{a^{\′}}+\sqrt{k_{\mathrm{DT}}}{\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}})}^2}{{(u_{\mathrm{DT}}^{a^{\′}}-{\mathrm{\μ}}_{D_2}^{a^{\′}})}^2}---\left(13\right)$

Visible, to a chromatographic column state of activation a ' timing of a certain filling state, D ₂-DT reaches the required column length of particular separation degree and is directly proportional to flow rate of carrier gas.And reaching particular separation degree, last flows out component T ₂the whole retention time t ' of minor _{r (T2}) as shown in formula (14):

$t_{R\left(T_2\right)}^{\′}=\frac{4R^2{e}^{c_1{a}^{\′}-c_2}{\mathrm{\μ}}_{T_2}^{a^{\′}}{(\sqrt{k_{D_2}}{\mathrm{\μ}}_{D_2}^{a^{\′}}+\sqrt{k_{\mathrm{DT}}}{\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}})}^2}{{({\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}}-{\mathrm{\μ}}_{D_2}^{a^{\′}})}^2}---\left(14\right)$

From formula (14), t ' _{r (T2)}irrelevant with flow rate of carrier gas.

The chromatographic column using for experiment has:

$t_{R\left(T_2\right)}^{\′}=\frac{4{\stackrel{\‾}{u}}^{\′\′}{R}^2{e}^{4.12803a^{\′}-0.69968}{\mathrm{\μ}}_{T_2}^{a^{\′}}{(\sqrt{k_{D_2}}{\mathrm{\μ}}_{D_2}^{a^{\′}}+\sqrt{k_{\mathrm{DT}}}{\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}})}^2}{4.5{({\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}}-{\mathrm{\μ}}_{D_2}^{a^{\′}})}^2}---\left(15\right)$

If approximate thinks:

$k_{D_2}\≈k_{\mathrm{DT}}=k---\left(16\right)$

$H_{\mathrm{eff}\left(D_2\right)}\≈H_{\mathrm{eff}\left(\mathrm{DT}\right)}=k\stackrel{\‾}{u}---\left(17\right)$

And D in chromatographic column when column cap is pressed as 200Kpa ₂effective plate height with represent, have:

$H_{\mathrm{eff}\left(D_2\right)}^{\′\′}={k\stackrel{\‾}{u}}^{\′\′}---\left(18\right)$

$t_{R\left(T_2\right)}^{\′}=\frac{4H_{\mathrm{eff}\left(D_2\right)}^{\′\′}{R}^2{e}^{4.12803a^{\′}-0.69968}{\mathrm{\μ}}_{T_2}^{a^{\′}}{({\mathrm{\μ}}_{D_2}^{a^{\′}}+{\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}})}^2}{4.5{({\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}}-{\mathrm{\μ}}_{D_2}^{a^{\′}})}^2}---\left(19\right)$

At flow rate of carrier gas be time, have:

$L=\frac{4H_{\mathrm{eff}\left(D_2\right)}^{\′\′}{R}^2{({\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}}+{\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}})}^2}{{({\mathrm{\μ}}_{\mathrm{DT}}^{a^{\′}}-{\mathrm{\μ}}_{D_2}^{a^{\′}})}^2}---\left(20\right)$

Draw D in chromatographic column according to formula (19), (20) ₂-DT separating degree is 1.5 o'clock, t ' _{r (T2)}with state of activation parameter a ' and flow rate of carrier gas time L and a ' relation.And from experimental result, predict very close with actual conditions.

As seen from Figure 6, a ' is larger, and required column length is shorter, and t ' _{r (T2)}have an extreme point with the graph of a relation (Fig. 7) of a ' is upper, a ' is between 0.4～0.5 time, t ' _{r (T2)}the shortest.The chromatographic peak tailing factor disclosing in associative list 9, with the rule of a ' increase, for obtaining better symmetrical peak, should be selected in extreme point left side lower activation degree and suitable long column length, although extend to some extent analysis time, the reliability of analyzing data can improve.

By above case, depress the situation of change of chromatographic column to hydrogen isotope gas retention according to the different states of activation and column cap, can obtain hydrogen isotope reduced mass μ and adjust retention time t ' _r, relative retention value r _i,sdeng relation, and introduced the parameter a ' that can characterize the fixing phase state of activation, and the parameter c relevant with fixing phase kind, phase ratio ₁, c ₂, set up t ' _rmathematical Modeling formula (8) with μ.Then required column length when having derived chromatogram hydrogen isotope gas being reached particular separation and spent, the whole retention time of minor and a ' and c based on this, ₁, c ₂deng relation.For the chromatographic column of the fixing phase of difference, as long as measure by experiment excursion and the c of a ' ₁, c ₂etc. parameter, just can estimate chromatographic column the fastest to the separation of hydrogen isotope gas under what state, thereby optimize chromatogram running parameter.Meanwhile, utilize this model, also can compare, evaluate fixing mutually and the quality prepared of chromatographic column, mutually fixing and chromatographic column preparation technology preferably had to a directive significance.

Under more excellent condition, the separation of hydrogen deuterium gaseous mixture can be realized in the chromatographic column 2.5min left and right of the present embodiment, and about 5.5min is with the interior separation realizing containing tritium gas, H while waiting peak height ₂-HD separating degree approximately 1.3～1.5, HD-D ₂separating degree approximately 2.0～2.2, D ₂-DT and DT-T ₂separating degree approximately 1.2～1.4.Thus, the single analyses time just can be controlled in the shorter time.

Above-described embodiment is only preferably one of implementation of the present invention; should be in order to not limit the scope of the invention; all changes of having no essential meaning of having done under body design thought of the present invention and spirit or the technical scheme of polishing; consistent with the present invention on its question essence solving, all should be within protection scope of the present invention.

Claims (10)

1. the preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis is used, is characterized in that, comprises the following steps:

S1: 4A molecular sieve is placed in to FeCl ₃in solution, soak this FeCl ₃and by part FeCl ₃the Fe (OH) that hydrolysis generates ₃and Fe (OH) ₃hydrate be all adsorbed on 4A molecular sieve; The order number of described 4A molecular sieve is 80～100 orders;

S2:4A molecular sieve adsorption FeCl ₃, Fe (OH) ₃and Fe (OH) ₃hydrate until saturated, then filtering FeCl ₃solution;

S3: absorption is had to FeCl ₃and Fe (OH) ₃and the 4A molecular sieve of hydrate puts in distilled water heating and boil, make FeCl ₃complete hydrolysis generates Fe (OH) ₃and hydrate adsorbed close are on 4A molecular sieve, adsorb unstable FeCl simultaneously ₃, Fe (OH) ₃and Fe (OH) ₃hydrate detach 4A molecular sieve;

S4: filter distilled water, and 4A molecular sieve is toasted, make the Fe (OH) on it ₃and hydrate dehydration generates Fe ₂o ₃;

S5: 4A molecular sieve is cooled to room temperature, and uses CO ₂passivation, obtains filler.

2. the preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis according to claim 1 is used, is characterized in that, in described step S1, takes 2～8 grams of 4A molecular sieves and is placed in FeCl ₃in solution, soak.

3. the preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis according to claim 2 is used, is characterized in that, in described step S1,4A molecular sieve is placed in to the FeCl of 200～300ml ₃in solution, soak 2～6h.

4. the preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis according to claim 3 is used, is characterized in that, in described step S1, and FeCl ₃solution is saturated solution.

5. the preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis according to claim 4 is used, is characterized in that, in described step S3,4A molecular sieve is put into 200～600ml distilled water and boil.

6. the preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis according to claim 5 is used, it is characterized in that, in described step S4,4A molecular sieve is put in baking oven and toasted, the temperature and time of baking is respectively 100～300 DEG C and 6～10h.

7. the preparation method of the gas-chromatography column packing that hydrogen isotope quantitative analysis according to claim 6 is used, is characterized in that, in described step S5, by 4A molecular sieve CO ₂passivation 4～8h.

8. the manufacture craft of gas chromatographic column, is characterized in that, comprises the following steps:

S1: the filler described in claim 1～7 any one is filled in stainless steel tube, and vibrations are tamped;

S2: utilize CO ₂mode with 3～5ml/min is carried out purge to stainless steel tube, and the purge time is 2～4h, then stainless steel tube is exposed in air more than 30 days;

S3: utilize pure Ne gas, in the mode of 8～5ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days, obtains chromatographic column.

9. the manufacture craft of gas chromatographic column, is characterized in that, comprises the following steps:

S1: the filler described in claim 1～7 any one is filled in stainless steel tube, and vibrations are tamped;

S2: utilize CO ₂mode with 3～5ml/min is carried out purge to stainless steel tube, and the purge time is 2～4h, then stainless steel tube is exposed in air more than 30 days;

S3: utilize pure Ne gas, in the mode of 8～10ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days;

S4: passing under the condition of pure Ne gas, stainless steel tube is heated to 200～300 DEG C, and maintains 3～5h;

S5: stainless steel tube temperature is down to room temperature, and uses by the Ne gas of water-vapo(u)r saturation, in the mode of 25～30ml/min, stainless steel tube is carried out to purge passivation 100～120h, obtain chromatographic column.

10. the manufacture craft of gas chromatographic column, is characterized in that, comprises the following steps:

S1: the filler described in claim 1～7 any one is filled in stainless steel tube, and vibrations are tamped;

S2: utilize CO ₂mode with 3～5ml/min is carried out purge to stainless steel tube, and the purge time is 2～4h, then stainless steel tube is exposed in air more than 30 days;

S3: utilize pure Ne gas, in the mode of 8～10ml/min, stainless steel tube is carried out to purge, the purge time is more than 7 days;

S4: passing under the condition of pure Ne gas, stainless steel tube is heated to 200～300 DEG C, and maintains 3～5h;

S5: stainless steel tube temperature is down to room temperature, and uses by the Ne gas of water-vapo(u)r saturation, in the mode of 25～30ml/min, stainless steel tube is carried out to purge passivation 100～120h;

S6: under the condition below 150 DEG C, by stainless steel tube heating 1～1.5h, and adopt pure Ne gas to carry out purge to stainless steel tube, repeat this step 1～3 time, obtain chromatographic column.