CN101210867A - Hydrodesulphurization catalyst activity measuring method and device for implementing the method - Google Patents

Abstract

The invention provides an in-situ vulcanization thermogravimetric analysis method and a method for determining hydrodesulfurization catalyst activity, and devices for implementing the methods. The in-situ vulcanization thermogravimetric analysis method comprises the following steps of: placing a sample to de analyzed into an in-situ vulcanization thermogravimetric analysis device with inert atmosphere; increasing the temperature of the sample to be analyzed to a first temperature with a first heating up speed, dehydrating with constant temperature, and decreasing the temperature to a second temperature; increasing the temperature of the sample to be analyzed to a third temperature with a second heating up speed, introducing H2 and H2S, and increasing the temperature to a fourth temperature with the second heating up speed, keeping at the fourth temperature for 0.5-2h, decreasing the temperature after a TG curve is stable, and obtaining the weighting percentage of the sample to be analyzed from the TG curve.

Description

The assay method of Hydrobon catalyst activity and the device of implementing described method

Technical field

The present invention relates to the assay method of a kind of original position heat of vulcanization reanalysis method, Hydrobon catalyst activity and the device of implementing described method, more particularly, relate to a kind of CoMo/ γ-Al ₂O ₃Be the assay method of Hydrobon catalyst original position heat of vulcanization reanalysis method, described catalyst activity and the device of implementing described method.

Background technology

Hydrodesulphurization is a very important technological process in the petroleum refining process, and it mainly acts on the sulfur impurity that is to remove in the oil product, makes product meet the specification requirement of vehicle fuel or the raw material of high-quality is provided for follow-up oil refining process.The Hydrobon catalyst of present industrial use is all made major catalyst with the sulfide of group vib metal M o or W basically, sulfide with VIII family metal Co or Ni is made promotor, adopt activated alumina or alumina silicate to make carrier, wherein the most frequently used catalyzer has: Co-Mo/ γ-Al ₂O ₃, Ni-Mo/ γ-Al ₂O ₃, Ni-W/ γ-Al ₂O ₃Deng.Generally believe that now its catalyticing mechanism is, catalyzer is through having formed MoS after the presulfurization ₂Crystalline phase, MoS ₂There is the sulphur room in the crystalline phase surface coordination on forming, and catalyzer sulphur room when contacting with sulfocompound combines with the sulphur atom of sulfocompound or the surface forms the S-S key, reaches the purpose of desulfurization.

The activity determination method of conventional hydrogenation catalyst is to utilize micro-reactor at H ₂S/H ₂Carry out presulfurization under the atmosphere earlier, feed model compound then and on catalyzer, carry out hydrodesulfurization reaction and investigate activity of such catalysts.But little devulcanization is long experimental period, needs the experimentation more than 4 hours, and can not obtain the direct experiment data of catalyst vulcanization degree.

Summary of the invention

The purpose of this invention is to provide a kind of method and apparatus that can measure the state of cure (vulcanization) of Hydrobon catalyst and the hydrodesulfurization activity of catalyzer (HDS) quickly and easily.

The invention provides a kind of original position sulfuration thermogravimetric (TG) analytical approach, this method comprises the steps:

Testing sample is placed the original position heat of vulcanization weight analysis device of inert atmosphere;

Testing sample is risen to first temperature and constant temperature dehydration with first programming rate, be cooled to second temperature then;

Testing sample is risen to the 3rd temperature with second programming rate, begin to feed H ₂And H ₂S, and continue to be warming up to the 4th temperature with second programming rate;

The 4th temperature constant temperature 0.5-2 hour, treat the steadily back cooling of TG curve, obtain the rate of body weight gain of testing sample by the TG curve.

The relative sulphidity of the rate of body weight gain calculation sample that can record by this method.

The present invention also provides a kind of original position heat of vulcanization weight analysis device that is used to implement original position heat of vulcanization reanalysis method of the present invention, and this device comprises thermogravimetric analysis device, H ₂Passage, H ₂S passage and inert gas passage, described passage links to each other H with the sample chamber of gas source with the thermogravimetric analysis device ₂, H ₂S and inert gas enter the thermogravimetric analysis device from gas source by described passage, and discharge from the gas vent of thermogravimetric analysis device.

In addition, the invention provides a kind of method of measuring the Hydrobon catalyst activity, this method comprises the steps:

(1), sets up HDS activity-relative sulphidity correlation models at concrete catalyzer and model compound;

(2) adopt original position heat of vulcanization reanalysis method, measure the relative sulphidity of catalyzer to be measured;

(3) calculate the HDS activity of catalyzer to be measured with the model of step (1) gained and the relative sulphidity of step (2) gained.

The present invention also provides a kind of device of measuring the Hydrobon catalyst activity, and this device comprises:

Little devulcanization device;

Original position heat of vulcanization weight analysis device of the present invention.

In a preferred embodiment, the device of mensuration Hydrobon catalyst activity of the present invention also comprises a DTU (Data Transfer unit) that links to each other with original position heat of vulcanization weight analysis device.

Original position heat of vulcanization reanalysis method of the present invention can access the direct experiment data of catalyst vulcanization degree.The method of mensuration Hydrobon catalyst activity of the present invention has been utilized original position heat of vulcanization reanalysis method, and it is compared with little devulcanization method of prior art has advantage fast, easily.

Description of drawings

Fig. 1 is the synoptic diagram of original position heat of vulcanization weight analysis experimental provision of the present invention.

Fig. 2 is Co-Mo/ γ-Al ₂O ₃The TG curve of catalyzer original position sulfuration.

Fig. 3 is little devulcanization schematic representation of apparatus that the present invention adopts, and wherein each equipment is respectively:

1 T-valve

2 reduction valve

3 retaining valves

4 mass-flow gas meters

5 heating furnaces (open and close type)

6 reactors

7 valves dorsad

8 device for absorbing tail gas

9 head tanks

10 pumps

Embodiment

In original position heat of vulcanization reanalysis method of the present invention, preferably realize inert atmosphere by nitrogen.First programming rate described in this method is in 8-12 ℃/min scope, and second programming rate is in 6-10 ℃/min scope; First temperature is in 280-320 ℃ of scope, and second temperature is in 60-100 ℃ of scope, and the 3rd temperature is in 130-170 ℃ of scope, and the 4th temperature is in 350-450 ℃ of scope.

The used device of the flow velocity of gas and original position heat of vulcanization reanalysis method is relevant, especially relevant with the volume of sample bin.H ₂, H ₂The flow of S is according to whole sample storehouse atmosphere (N ₂+ H ₂+ H ₂S) their shared concentration decides in, general H ₂The S mass concentration is not less than 1% and gets final product H ₂The concentration height of should trying one's best, N ₂Be protection air-flow (the protection instrument is not corroded), N ₂Air-flow is greatly then favourable to service life of equipment.When adopting the TA 951 type thermogravimetric analyzers (its sample bin volume is 80ml) of for example instrument company of Du Pont manufacturing, H ₂And H ₂The flow velocity of S respectively in 5-15ml/min and 2-4ml/min scope, N ₂Flow velocity in the 40-60ml/min scope.

The sample of available original position heat of vulcanization reanalysis method of the present invention analysis is the known Hydrobon catalyst of prior art, for example make major catalyst, make promotor, adopt activated alumina or alumina silicate to make the Hydrobon catalyst, particularly CoMo/ γ-Al of carrier with the sulfide of VIII family metal Co or Ni with the sulfide of group vib metal M o or W ₂O ₃Series catalysts, for example Co-Mo/ γ-Al ₂O ₃, Ni-Mo/ γ-Al ₂O ₃, Ni-W/ γ-Al ₂O ₃Deng.

In original position heat of vulcanization reanalysis method of the present invention, the sample rate of body weight gain can be read from the TG curve, and the output data that can be used as original position heat of vulcanization weight analysis device exports the data input port of the DTU (Data Transfer unit) that is attached thereto to.The relative sulphidity of sample equals the ratio of sample rate of body weight gain and the theoretical rate of body weight gain of sample.Be the relative sulphidity of calculation sample, need the at first theoretical rate of body weight gain of calculation sample.Be the computing method that example illustrates theoretical rate of body weight gain with the Co-Mo catalyzer below:

The Co-Mo catalyzer is with initial oxidation attitude CoO and MoO ₃Form exists, and wherein the percentage by weight of CoO is 20%, MoO ₃Percentage by weight be 4.7%, all the other are alumina support.The sulfuration end product is MoS ₂And Co ₉S ₈, then this catalyzer is MoS by final sulfur product ₂And Co ₉S ₈The theoretical rate of body weight gain that calculates is 3.002%.

Fig. 1 is a synoptic diagram of original position heat of vulcanization weight analysis device of the present invention.In original position heat of vulcanization weight analysis device of the present invention, the thermogravimetric analysis device can adopt the known conventional equipment of prior art, for example the TA 951 type thermogravimetric analyzers of instrument company of Du Pont manufacturing.H ₂, N ₂And H ₂The pipeline of S gas is connected with the thermogravimetric analysis device.This original position heat of vulcanization weight analysis device also can comprise a gas recovery and circulating device.

In the step (1) of mensuration Hydrobon catalyst activity methods of the present invention, adopt following step to set up HDS activity-relative sulphidity correlation models:

The a series of catalyst sample C of preparation under different condition ₁, C ₂, C ₃... C _n

Adopt original position heat of vulcanization weight analysis device that above-mentioned catalyst sample is vulcanized, and measure the relative sulphidity S of each catalyst sample ₁, S ₂, S ₃... S _n

Adopt micro-reactor to measure above-mentioned catalyst sample at the active H of the HDS of particular model compound ₁, H ₂, H ₃... H _n

Obtain HDS activity-relative sulphidity correlation models:

H＝a×S+b (I)

Wherein $a=\frac{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}(S_i-\stackrel{\‾}{S})(H_i-\stackrel{\‾}{H})}{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{(S_i-\stackrel{\‾}{S})}^2}---\left(\mathrm{II}\right)$

$b=\stackrel{\‾}{H}-a\stackrel{\‾}{S}---\left(\mathrm{III}\right)$

Wherein $\stackrel{\‾}{S}=\frac{1}{n}\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{S}_i---\left(\mathrm{IV}\right),$ $\stackrel{\‾}{H}=\frac{1}{n}\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{H}_i---\left(V\right).$

Be used to set up that the HDS activity-catalyst sample of sulphidity correlation models should prepare under different conditions relatively, the quantity of the catalyst sample for preparing under different condition is at least 3, is preferably at least 4.Described different condition can be different activating treatment temperature, activation processing time or metal carrying capacity.The HDS activity of catalyzer can be represented with the conversion ratio of model compound.

Model compound described in the present invention comprises thiophene, benzothiophene, dimethyl Dibenzothiophene etc., and is common in other sulfocompounds in the petroleum products.

The sample of the methods analyst of available mensuration Hydrobon catalyst activity of the present invention is the known Hydrobon catalyst of prior art, for example make major catalyst, make promotor, adopt activated alumina or alumina silicate to make the Hydrobon catalyst, particularly CoMo/ γ-Al of carrier with the sulfide of VIII family metal Co or Ni with the sulfide of group vib metal M o or W ₂O ₃Series catalysts, for example Co-Mo/ γ-Al ₂O ₃, Ni-Mo/ γ-Al ₂O ₃, Ni-W/ γ-Al ₂O ₃Deng.

Fig. 3 can be used for a kind of little devulcanization schematic representation of apparatus of the present invention.Concrete mensuration process is: catalyst sample to be measured and silica sand are mixed, place in the reactor constant temperature zone, remainder filling silica sand; With sulfurized oil (5%CS ₂+ cyclohexane) sulfuration is 3 hours, switch to after sulfuration finishes reaction oil (0.45%4,6-dimethyl Dibenzothiophene (4,6-DMDBT)+decane), stable reaction is sample analysis after 3 hours.Calculate conversion ratio, activity of such catalysts and the selectivity of course of reaction by analytical reactions product and remaining model compound.

In the device of mensuration activity of hydrocatalyst of the present invention, described DTU (Data Transfer unit) can be achieved as follows function at least: set a in the above-mentioned formula (I) and the value of b, input data S calculates and output data H.This function can realize by conventional means of the prior art.

Embodiment

Reagent and instrument

Co-Mo/ γ-the Al of series oxidation state ₂O ₃Catalyzer and γ-Al ₂O ₃Provide by Research Institute of Petro-Chemical Engineering hydrogenation catalyst research department; 99.9%H ₂S gas provides high-purity H by sea, Beijing spectrum gas company limited ₂, N ₂From Research Institute of Petro-Chemical Engineering's Gas Plant.

TA 951 type thermogravimetric analyzers, instrument company of Du Pont makes.

The catalyst sample preparation

The carrier that TG analytic sample: D1, D2, D3 and four catalyst samples of D4 adopt is Al ₂O ₃, maceration extract is ammonium molybdate, cobalt nitrate.After adopting the saturated dipping active component in hole on the carrier, respectively at 90 ℃, 200 ℃, 250 ℃ and 300 ℃ of following activation processing 3h.The metal carrying capacity of four catalyst samples is identical, and the percentage by weight of CoO is 20%, MoO ₃Percentage by weight be 4.7%.

Original position heat of vulcanization weight analysis device and sulfidation

Fig. 1 is thermogravimetric analysis original position vulcanization plant figure.Under high purity nitrogen atmosphere, earlier each catalyst sample is warming up to 300 ℃ with the programming rate of 10 ℃/min, constant temperature 30min dehydration is cooled to 80 ℃ then, and the programming rate with 8 ℃/min is warming up to 400 ℃ again, and begins to feed H when being warming up to 150 ℃ ₂And H ₂S, H ₂Flow is 10ml/min, H ₂The S flow is 3ml/min.Constant temperature 1 hour again after arriving 400 ℃ is treated the steadily back cooling of TG curve.Co-Mo/ γ-Al of the different preparation methods of The effects ₂O ₃Catalyzer is at H ₂S/H ₂TG behavior under the atmosphere, and with pure γ-Al ₂O ₃Reference is made in the TG behavior of carrier under same experimental conditions.Fig. 2 is the wherein TG curve that records.The rate of body weight gain of each catalyst sample and relative sulphidity see Table 1.

The mensuration of catalyst hydrogenation desulfurization micro-activity

Reaction unit is seen Fig. 3.40-60 purpose catalyst sample 0.15g and 40-60 order silica sand 1g are evenly mixed, place in the reactor constant temperature zone, remainder filling silica sand.Condition is vulcanized 3h routinely.Sulfuration switches to reaction oil (0.45%4, the 6-DMDBT+ decane) after finishing.Sample analysis behind the stable reaction 3h.4, the 6-DMDBT conversion ratio sees Table 1.

The relative sulphidity of the HDS activity of table 1 catalyzer and TG sulfuration

Catalyzer	Vulcanize rate of body weight gain (%) before 400 ℃	Sulphidity (S) (%) relatively	The HDS activity (with 4, represent, %) by the 6-DMDBT conversion ratio
				D1	2.594	86.41	34.79
D2	3.039	101.23	38.15
				D3	3.127	104.16	39.75
D4	3.250	108.26	40.26

Set up model

According to formula (IV) and formula (V), obtain S=100.02 by the data in the table one, H=38.24.

According to formula (II) and formula (III), obtain a=0.2567, b=12.56.

Obtaining HDS activity-relative sulphidity correlation models thus is:

H＝0.2567S+12.56

Measure the relative sulphidity of catalyzer to be measured and calculate its HDS activity

Get a catalyst sample D to be measured, record its 400 ℃ with said method before sulfuration weightening finish be 3.100%, sulphidity is 103.26% relatively.Therefore the HDS activity of this catalyzer is 0.2567 * 103.26+12.56=39.07.

Claims (13)

1. original position heat of vulcanization reanalysis method comprises:

Testing sample is placed the original position heat of vulcanization weight analysis device of inert atmosphere;

Testing sample is risen to first temperature and constant temperature dehydration with first programming rate, be cooled to second temperature then;

Testing sample is risen to the 3rd temperature with second programming rate, begin to feed H ₂And H ₂S, and continue to be warming up to the 4th temperature with second programming rate;

The 4th temperature constant temperature 0.5-2 hour, treat the steadily back cooling of TG curve, obtain the rate of body weight gain of testing sample by the TG curve.

2. the method for claim 1 is characterized in that realizing described inert atmosphere with nitrogen.

3. the method for claim 1 is characterized in that described first programming rate in 8-12 ℃/min scope, and second programming rate is in 6-10 ℃/min scope; First temperature is in 280-320 ℃ of scope, and second temperature is in 60-100 ℃ of scope, and the 3rd temperature is in 130-170 ℃ of scope, and the 4th temperature is in 350-450 ℃ of scope.

4. the process of claim 1 wherein that described testing sample is selected from the sulfide of Mo or W makes major catalyst, makes promotor, adopts activated alumina or alumina silicate to make the Hydrobon catalyst of carrier with the sulfide of Co or Ni.

5. the method for claim 4, wherein said testing sample is selected from Co-Mo/ γ-Al ₂O ₃, Ni-Mo/ γ-Al ₂O ₃With Ni-W/ γ-Al ₂O ₃

6. original position heat of vulcanization weight analysis device, this device comprises thermogravimetric analysis device, H ₂Passage, H ₂S passage and inert gas passage, described passage links to each other the sample chamber of gas source with the thermogravimetric analysis device.

7. method of measuring the Hydrobon catalyst activity comprises:

(1), sets up HDS activity-relative sulphidity correlation models at concrete catalyzer and model compound;

(2) adopt original position heat of vulcanization reanalysis method, measure the relative sulphidity of catalyzer to be measured;

(3) calculate the HDS activity of catalyzer to be measured with the model of step (1) gained and the relative sulphidity of step (2) gained.

8. the method for claim 7 is characterized in that step (1) wherein comprising:

The a series of catalyst sample C of preparation under different condition ₁, C ₂, C ₃... C _n

Adopt original position heat of vulcanization weight analysis device that above-mentioned catalyst sample is vulcanized, and measure the relative sulphidity S of each catalyst sample ₁, S ₂, S ₃... S _n

Adopt micro-reactor to measure above-mentioned catalyst sample at the active H of the HDS of particular model compound ₁, H ₂, H ₃... H _n

Obtain HDS activity-relative sulphidity correlation models:

H＝a×S+b (I)

Wherein $a=\frac{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}(S_i-\stackrel{\‾}{S})(H_i-\stackrel{\‾}{H})}{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{(S_i-\stackrel{\‾}{S})}^2}---\left(\mathrm{II}\right)$

b＝H-aS (III)

Wherein $\stackrel{\‾}{S}=\frac{1}{n}\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{S}_i---\left(\mathrm{IV}\right),$ $\stackrel{\‾}{H}=\frac{1}{n}\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{H}_i---\left(V\right).$

9. claim 7 or 8 method is characterized in that described model compound is selected from thiophene, benzothiophene, dimethyl Dibenzothiophene and is common in other sulfocompounds in the petroleum products.

10. claim 7 or 8 method, wherein said catalyzer to be measured is selected from the sulfide of Mo or W and makes major catalyst, makes promotor, adopts activated alumina or alumina silicate to make the Hydrobon catalyst of carrier with the sulfide of Co or Ni.

11. the method for claim 10, wherein said catalyzer to be measured is selected from Co-Mo/ γ-Al ₂O ₃, Ni-Mo/ γ-Al ₂O ₃With Ni-W/ γ-Al ₂O ₃

12. a device of measuring the Hydrobon catalyst activity, this device comprises:

Little devulcanization device;

Original position heat of vulcanization weight analysis device.

13. the device of claim 12, it is characterized in that also comprising the DTU (Data Transfer unit) that links to each other with described original position heat of vulcanization weight analysis device, described DTU (Data Transfer unit) can be achieved as follows function at least: a in the setting formula (I) and the value of b, input data S calculates and output data H.

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