CN102435463B - Online acquisition system and method for catalyst slurry - Google Patents
Online acquisition system and method for catalyst slurry Download PDFInfo
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- CN102435463B CN102435463B CN201110338561.9A CN201110338561A CN102435463B CN 102435463 B CN102435463 B CN 102435463B CN 201110338561 A CN201110338561 A CN 201110338561A CN 102435463 B CN102435463 B CN 102435463B
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- 239000002002 slurry Substances 0.000 title claims abstract description 95
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- 238000010438 heat treatment Methods 0.000 claims description 30
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- 238000012806 monitoring device Methods 0.000 claims description 17
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- 239000012429 reaction media Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 abstract description 7
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
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- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The invention relates to an online acquisition system and an online acquisition method for catalyst slurry. The online acquisition system for the catalyst slurry comprises (A) a sampling system, and (B) an inert medium injection system, wherein the sampling system comprises a first sampling pipeline (14), a second sampling pipeline (16) and a catalyst slurry collecting container (11); the first end of the first sampling pipeline (14) extends into a slurry reactor (8); the first sampling pipeline (14) is provided with a first valve (6); the second end of the second sampling pipeline (16) is connected to the second end of the first sampling pipeline; the second sampling pipeline (16) is provided with a second valve (7) and a third valve (10); the catalyst slurry collecting container (11) is connected to the first end of the second sampling pipeline (16); the inert medium injection system comprises an inert liquid medium supply device (1) and a fourth pipeline (12); and the inert liquid medium supply device (1) is connected to the second ends of the first sampling pipeline (14) and the second sampling pipeline (16). The system can easily acquire catalyst slurry on line.
Description
Technical field
The present invention relates to a kind of catalyst slurry on-line acquisition system and method, relate in particular to catalyst slurry on-line acquisition system and method in Fischer-Tropsch synthetic pulp state bed reactor.
Background technology
Fischer-Tropsch is synthetic to be referred under certain conditions, synthetic gas CO and H
2the reaction of synthetic hydrocarbon under the effect of catalyzer.From the 1950's, realize coal-based synthetic liquid fuel heavy industrialization (Dry, M.E., Catalysis Today, 1990,6 (3) 183-206) in South Africa Sasol company.What Fischer-Tropsch synthesized normal employing is cobalt-base catalyst and ferrum-based catalyst, and the reactor of employing has fixed bed reactors, flowing bed reactor and paste state bed reactor.The hydrogen-carbon ratio requirement of cobalt-base catalyst based on in synthetic gas, being more suitable for rock gas is that the Fischer-Tropsch that synthesizes source of the gas synthesizes.Ferrum-based catalyst, owing to possessing water-gas shift activity, is that the fischer-tropsch reaction that synthesizes source of the gas all can use to rock gas or coal.Because paste state bed reactor has higher production efficiency, catalyzer is easy to handling and can be directly used in the coal based synthetic gas that hydrogen-carbon ratio is lower, demonstrate larger advantage, be the synthetic liquid fuel technology of giving priority to both at home and abroad at present.
For the ferrum-based catalyst of paste state bed reactor, must possess certain particle size and wear strength, could in fischer-tropsch reaction process, keep certain stability to separate with one-tenth wax with being beneficial to main reaction product.In recent years, most research work all concentrates on formula and the technology of preparing of catalyzer, as South Africa Sasol company discloses the preparation method of syrup state bed Fischer Tropsch synthesis iron base catalyst in patent WO99/49965, Shenhua Group discloses formulation adjuvant research and the fabricating technology research of slurry state bed catalyst ferrum-based catalyst in the patents such as CN101293206B, CN101298046A and CN101884926A, and the object of these researchs is all the abrasion resistance for improving catalyzer.Simultaneously, with regard to ferrum-based catalyst activating process and technique for applying in slurry state bed, also done both at home and abroad a large amount of work, as Chinese patent application CN1583274, CN101796166A and CN10189206A etc. disclose the impact of the performance such as oily space-time yield, deactivation rate of activating process parameter on catalyzer.
But ferrum-based catalyst is in paste state bed reactor, from reduction, reaction until inactivation, all there is very complicated variation from appearance, size and phase.Therefore to improve catalyzer resistance to abrasion and stability in slurry state bed, must gather the catalyzer in course of reaction, follow the tracks of the physical and chemical properties change of catalyzer.And in research work both at home and abroad, rarely report the Fischer-Tropsch synthetic pulp state bed catalyst method of sampling and system.
The patent No. is that the Chinese patent that the name of ZL90214227.5 (CN2072151U) is called " a kind of high temperature, high-pressure sampling container " discloses a kind of sampling equipment that can be used for high temperature, high pressure and deep well sampling, but this sampling equipment is only applicable to the steam sampling of high temperature, high pressure and deep well, in its sample of getting, do not contain solid particle, can not cause wearing and tearing to sampler, and it is simple in structure, therefore,, in syrup state bed Fischer Tropsch synthetic reaction process, cannot sample with described sampling container.
The Chinese patent that the name of number of patent application 96193860.9 (CN1184529A) is called " sampling method and device " discloses the method and apparatus sampling in the streaming suspension that a kind of polymer beads from olefinic polymerization and hydrocarbon diluent form, but this method is only applicable to the situation that temperature and pressure is lower, be not suitable for the situation of the synthetic middle temperature of Fischer-Tropsch, middle pressure, therefore, in syrup state bed Fischer Tropsch synthetic reaction process, cannot carry out the sampling of catalyst slurry by described sampling method and system equally.
Therefore, need a kind of method and system of carrying out online the sampling of catalyst slurry in syrup state bed Fischer Tropsch synthetic reaction process.
Summary of the invention
The present invention relates to a kind of catalyst slurry on-line acquisition system, wherein catalyst slurry is contained in paste state bed reactor (8), comprising:
(A) sampling system, comprising:
(A1) the first sampling pipeline, has first end and the second end, and the first end of the first sampling pipeline extend into slurry state bed
In reactor, wherein, on the first sampling pipeline, be provided with the first valve;
(A2) the second sampling pipeline, has first end and the second end, and the second end of the second sampling pipeline is connected to first and adopts
The second end of sample pipeline; Wherein, be provided with second valve at the second end place of the second sampling pipeline, first of the second sampling pipeline
End place is provided with the 3rd valve;
(A3) catalyst slurry collection container, is connected to the first end of the second sampling pipeline;
(B) inert media injected system, comprising:
(B1) inertia liquid medium feeding mechanism; With
(B2) the 4th pipeline, is connected to the second end of the first sampling pipeline and the second end of the second sampling pipeline by inertia liquid medium feeding mechanism, wherein on the 4th pipeline, is provided with the 4th valve.
Preferably, (A) sampling system further comprises: (A4) pressure monitoring device, is connected on the sampling of second between second valve and the 3rd valve pipeline by the 3rd pipeline.
Preferably, in the 3rd pipeline, be provided with U-shaped pipe, in U-shaped pipe, fill inertia liquid medium.
Preferably, inert media injected system further comprises: (B3) pump, is arranged between the 4th valve and inertia liquid medium feeding mechanism.
Preferably, (B) inert media injected system further comprises: (B4) pressure monitoring device, is arranged between pump and the 4th valve.
Preferably, catalyst slurry on-line acquisition system further comprises:
(C) purging system, comprising:
(C1) inert blowing gas sweeping device, is connected to the second end of the second sampling pipeline by the 5th pipeline;
(C2) the 5th valve, is arranged on the 5th pipeline.
Preferably, (A) pipeline and the valve in sampling system is wear-resistant pipeline and wear-resisting valve.
Preferably, (B) pressure monitoring device in inert media injected system and (A) pressure monitoring device in sampling system be tensimeter.
Preferably, (A) pipeline and the valve outside paste state bed reactor is provided with heating arrangement or heating device in sampling system, (B) inert media injected system.
Preferably, paste state bed reactor is Fischer-Tropsch synthetic pulp state bed reactor; Inertia liquid medium feeding mechanism is liquid wax feeding mechanism.
The invention still further relates to a kind of catalyst slurry online acquisition method, undertaken by system of the present invention, the method comprises:
(a) close the 3rd valve, open the first valve and second valve, make catalyst slurry in paste state bed reactor enter (A1) first sampling pipeline and (A2) the second sampling pipeline;
(b) close second valve, open the 3rd valve, catalyst slurry is collected in (A3) catalyst slurry collection container;
Alternatively, (c) repeating step (a) to (b).
Preferably, inertia liquid medium is identical with reaction medium or product in paste state bed reactor.
Preferably, the pressure in paste state bed reactor is greater than external environment condition pressure, and preferably, with respect to external environment condition pressure, the pressure in paste state bed reactor is 0.4-3.5MPa, is preferably 0.5-3.0MPa.
Preferably, in paste state bed reactor, temperature is 200～320 ℃, preferably 200-300 ℃, more preferably 235～275 ℃.
Preferably, further comprise: in step (a) before, (a ') by (B) inert media injected system, inert media is injected in paste state bed reactor until in paste state bed reactor liquid level higher than the first end preset distance H of the first sampling pipeline.
Preferably, in the time that system has heating arrangement or heating device, the heating-up temperature of heating arrangement or heating device or companion's hot temperature degree are 100～200 ℃.
Preferably, the method further comprises: (d) cleaning step: in the first sampling pipeline and the second sampling pipeline, inject inertia liquid medium by (B) inert media injected system, clean.
Preferably, in the time that catalyst slurry on-line acquisition system comprises (C) purging system, the method further comprises: (e) purge step: by purging system, the second sampling pipeline (is purged.
Preferably, the mode of collection catalyst slurry is batch (-type).
Preferably, catalyst slurry online acquisition method is the catalyst slurry online acquisition method in fischer-tropsch synthetic catalyst reduction phase or Fischer-Tropsch synthesis stage.
This system is the catalyst slurry in online acquisition paste state bed reactor easily.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of a kind of preferred implementation of sampling system of the present invention.
Embodiment
In the present invention, the in the situation that of contradiction not or conflict, all embodiment of the present invention, embodiment and feature can combine mutually.
In the present invention, conventional unit, parts etc., both can be purchased, also can be according to content self-control disclosed by the invention.
In the present invention, for outstanding emphasis of the present invention, the omission that the operation to some routines and unit, parts carry out, or only do simple description.
In the present invention, " with ... be connected " or " being connected to " or " connection ", can be both that the two is directly connected, also can such as, be connected or connect across common parts or device (valve, pump, heat interchanger etc.).
In the present invention, term " on-line acquisition system " refers to the system that equipment gathers the in the situation that of operation, for example, in normal situation of producing, as fischer-tropsch synthetic catalyst reduction phase or Fischer-Tropsch synthesis stage.
One aspect of the present invention relates to the catalyst slurry on-line acquisition system in paste state bed reactor, and this system comprises:
(A) sampling system, comprising:
(A1) the first sampling pipeline, has first end and the second end, and the first end of the first sampling pipeline extend in paste state bed reactor, wherein, on the first sampling pipeline, is provided with the first valve;
(A2) the second sampling pipeline, has first end and the second end, and the second end of the second sampling pipeline is connected to the second end of the first sampling pipeline; Wherein, be provided with second valve at the second end place of the second sampling pipeline, the first end place of the second sampling pipeline is provided with the 3rd valve;
(A3) catalyst slurry collection container, is connected to the first end of the second sampling pipeline.
Preferably, sampling system further comprises: (A4) pressure monitoring device, is connected to the second sampling pipeline between second valve and the 3rd valve by the 3rd pipeline.Preferably, (A4) pressure monitoring device is tensimeter.
Preferably, in the 3rd pipeline, be provided with U-shaped pipe, in U-shaped pipe, fill inertia liquid medium.Can prevent that like this in sampling process, slurries enter the pipeline before pressure monitoring device, result in blockage.
Preferably, (A3) catalyst slurry collection container is catalyst slurry holding tank.
Between the first end of the first sampling pipeline and the second end, be provided with the first valve.Preferably, the first valve and/or second valve are ball valve.Preferably, the 3rd valve is stop valve.
Preferably, (A) pipeline and the valve in sampling system all has abrasion resistance.(A) pipeline in sampling system and valve adopt wear-resistant pipeline and valve, can increase the service life, and save maintenance cost.
Preferably, the pressure in paste state bed reactor is greater than external environment condition pressure.
Preferably, paste state bed reactor is Fischer-Tropsch synthetic pulp state bed reactor.
Preferably, the system that line acquisition system of the present invention gathers the catalyzer of reduction or the stage of reaction, the system that particularly preferably catalyzer of the synthetic reduction of Fischer-Tropsch or the stage of reaction gathers.
Preferably, in paste state bed reactor, temperature is 200～320 ℃, preferably 200-300 ℃, more preferably 235～275 ℃.Preferably, in paste state bed reactor, pressure is 0.4-3.5MPa, is preferably 0.5-3.0MPa (relative pressure, gauge pressure).With respect to external environment condition pressure, relative pressure in paste state bed reactor (gauge pressure) is 0.4-3.5MPa, is preferably 0.5-3.0MPa.Preferably, when the reduction of paste state bed reactor inner catalyst or reaction, temperature is 200～320 ℃, preferably 200-300 ℃, more preferably 235～275 ℃.Preferably, when the reduction of paste state bed reactor inner catalyst or reaction, pressure is 0.4-3.5MPa, is preferably 0.5-3.0MPa.
The major product (hydrocarbon products) that Fischer-Tropsch synthetic pulp state bed reactor of the present invention is produced is hydrocarbon gas (containing low-carbon alkene), light naphthar and heavy naphtha, diesel oil distillate, wax and synthetic water, especially with naphtha, diesel oil distillate and wax primary product.In the time producing, paste state bed reactor top is gas phase zone, Wei Jiangtaichuan district, bottom.
The wax of producing in Fischer-Tropsch synthesis device passes through to discharge as product after the interior filtrator arranging of reactor and catalyst separation, after also can separating with catalyst granules by external equipment for separating liquid from solid by the slurries in extraction device, obtains.In external filter situation, separate the catalyst granules obtaining and again loop back reactor continuation participation reaction.
Preferably, (A3) catalyst slurry collection container is high-temperature resistant container, for example stainless steel or glass container.
Preferably, on-line acquisition system of the present invention further comprises:
(B) inert media injected system, comprising:
(B1) inertia liquid medium feeding mechanism; With
(B2) the 4th pipeline, is connected to the second end of the first sampling pipeline and the second end of the second sampling pipeline by inertia liquid medium feeding mechanism, wherein on the 4th pipeline, is provided with the 4th valve.
Preferably, (B) inert media injected system further comprises: (B3) pump, is arranged between the 4th valve and inertia liquid medium feeding mechanism.Preferably, (B3) pump is reciprocating pump.
Preferably, inert media injected system further comprises: (B4) pressure monitoring device, is arranged between (B3) pump and the 4th valve.(B4) pressure monitoring device is for measuring the pressure of the 4th pipeline.Preferably, (B4) pressure monitoring device is tensimeter.Preferably, (B4) pressure monitoring device is arranged on (B3) delivery side of pump place.
Preferably, the 4th valve is ball valve.Preferably, between (B4) pressure monitoring device and the 4th valve, be provided with the 6th valve.Preferably, the 6th valve is stop valve.
Preferably, inertia liquid medium is for example, with reaction medium (solvent) or product in paste state bed reactor identical.Like this, just can Jiang Taichuan district liquid level is lower in paste state bed reactor time, do not affect reaction to injecting inertia liquid medium in paste state bed reactor, reduce or avoid polluting reaction, without separating in addition inertia liquid medium.
(B1) inertia liquid medium feeding mechanism is used for supplying liquid medium.For example, (B1) inertia liquid medium feeding mechanism is the liquid medium storage device of inertia, and the liquid media storage tank of for example inertia, as liquid wax storage tank.
Preferably, inertia liquid medium is liquid wax.Preferably, (B1) inertia liquid medium feeding mechanism is liquid wax feeding mechanism.In the time that paste state bed reactor is Fischer-Tropsch synthetic pulp state bed reactor, because product comprises wax, particularly preferably inertia liquid medium is liquid wax.
Preferably, on-line acquisition system of the present invention further comprises:
(C) purging system, comprising:
(C1) inert blowing gas sweeping device, is connected to the second end of the second sampling pipeline by the 5th pipeline;
(C2) the 5th valve, is arranged on the 5th pipeline.
Preferably, (C1) inert blowing gas sweeping device is connected to the second end of the first sampling pipeline and the second end of the second sampling pipeline by the 5th pipeline.
Preferably, part, second sampling pipeline, three pipeline, first valve, second valve and three valve of the first sampling pipeline outside reactor is provided with heating arrangement or heating device, preferably electric heat tracing device, for example electric-heating belt.For example, at normal temperature (20～30 ℃) lower when solid-state when the composition in catalyst slurry or inertia liquid medium, for example, when inertia liquid medium is liquid wax, heating arrangement or heating device can prevent that liquid wax from condensing in the place of flowing through or solidify.Therefore, preferably, in this case, pipeline or equipment outside all reactors of the liquid MEDIA FLOW warp of inertia are provided with above-mentioned heating arrangement or heating device.Preferably, pipeline and the valve outside all reactors of on-line acquisition system of the present invention is provided with above-mentioned heating arrangement or heating device.Preferably, except purging system, pipeline and valve outside all reactors of on-line acquisition system of the present invention are provided with above-mentioned heating arrangement or heating device.For example, (A) pipeline and the valve outside all reactors is provided with above-mentioned heating arrangement or heating device in sampling system, (B) inert media injected system.
Preferably, the heating-up temperature of heating arrangement or heating device or companion's hot temperature degree are 100～200 ℃.
The present invention relates to use system of the present invention on the other hand to the catalyst slurry online acquisition method in paste state bed reactor, comprises the following steps:
(a) the 3rd valve cuts out, open the first valve and second valve, make catalyst slurry in paste state bed reactor enter (A1) first sampling pipeline and (A2) the second sampling pipeline;
(b) when the pressure in the second sampling pipeline is identical with paste state bed reactor internal pressure, close second valve, open the 3rd valve, catalyst slurry is collected in (A3) catalyst slurry collection container.
Alternatively, (c) repeating step (a) to (b).
For successfully sampling, (A1) port of the first end of the first sampling pipeline should for example, lower than the liquid level certain distance in paste state bed reactor, preset distance H.For example, preset distance H=15～50mm, preferably 15～30mm, for example about 20mm.
Preferably, when the distance between the liquid level in port and the paste state bed reactor of the first end of (A1) first sampling pipeline does not reach while requiring, for example higher than the first end of the first sampling pipeline (14) higher than liquid level, although or the first end of the first sampling pipeline is lower than liquid level, but while being less than preset distance H, by (B) inert media injected system, inert media is injected in paste state bed reactor until in paste state bed reactor liquid level reach requirement, for example, higher than the first end preset distance H of the first sampling pipeline (14).
Therefore, preferably, method of the present invention further comprises: in step (a) before,
(a ') by (B) inert media injected system, inert media is injected in paste state bed reactor until in paste state bed reactor liquid level reach requirement, for example, higher than distance H.
Preferably, step (a ') comprising: close the first valve, second valve and the 5th valve (if existence), start (B3) pump, after the pressure in the 4th pipeline for example, higher than paste state bed reactor (about 0.5MPa), open the first valve, in paste state bed reactor, inject inertia liquid medium, until liquid level reaches requirement in paste state bed reactor.
Preferably, in step (a) before, preferably in step (a ') before, confirm whether heating arrangement or the heating device in (A) sampling system reaches design temperature.When the composition in catalyst slurry or or inertia liquid medium for example, at normal temperature (20～30 ℃) lower when solid-state, before sampling, need to confirm (A) sampling system and (B) heating arrangement or the heating device in inert media injected system whether reach design temperature.
Preferably, method of the present invention further comprises:
(d) cleaning step: inject inertia liquid medium by (B) inert media injected system in the first sampling pipeline and the second sampling pipeline, clean.
Preferably, (d) cleaning step comprises: start (B3) pump, open the 6th valve (if exist), the 4th valve, second valve, the 3rd valve, to filling liquid paraffin in the first sampling pipeline and the second sampling pipeline, clean.
Preferably, after (d) cleaning step, also comprise purge step.Therefore, preferably, method of the present invention further comprises:
(e) purge step: the second sampling pipeline is purged by purging system.
After cleaning, stop (B3) pump, close the 4th valve, for example, by purging inert gas (nitrogen) by purging system from the 5th valve, sampling pipeline is purged to (for example 5 minutes).
After purging, close the 5th valve and the 3rd valve.
With reference to the accompanying drawings, as an example of Fischer-Tropsch synthetic pulp state bed reactor example, the system and method for online acquisition catalyst slurry of the present invention is described in detail.
The present invention relates to a kind of method of Fischer-Tropsch synthetic pulp state bed reactor online acquisition catalyst slurry, it is characterized in that the catalyzer of the synthetic reduction of Fischer-Tropsch or the stage of reaction to gather, follow the tracks of the physical and chemical properties change of catalyzer.Under certain temperature, pressure and catalyst slurry concentration, in reaction gas, pass into unstripped gas, make catalyst reduction or Fischer-Tropsch synthesis occurs; Reaction product and unreacted gas, by after still internal filter, enter piece-rate system and separate; In reduction or course of reaction, by sampling apparatus and system, gather catalyst slurry.
As shown in Figure 1, one preferred embodiment in, catalyst slurry acquisition system provided by the invention comprises:
(A) sampling system, comprising: the first sampling pipeline 14 and on the 5th valve (ball valve) 5 and the first valve (ball valve) 6, the second sampling pipeline 16 and on second valve (ball valve) 7, the 3rd valve (stop valve) 10 and tensimeter 18, catalyst slurry holding tank 11.Preferably, part, first valve (ball valve) 6, second sampling pipeline 16, second valve (ball valve) 7 and three valve (stop valve) 10 of the first sampling pipeline 14 outside reactor all adds electric-heating belt.Preferably, filled with liquid paraffin in the U-shaped pipe before tensimeter 18, prevent in sampling process slurries enter tensimeter before pipeline result in blockage.
(B) liquid wax injected system, comprising: the 6th valve (stop valve) 3, the 4th valve (ball valve) 4 and tensimeter 17 on liquid wax accumulator tanks 1, liquid wax injection pump 2, the 4th pipeline (liquid wax injects pipeline) 12 and the 4th pipeline 12.
Preferably, catalyst slurry acquisition system of the present invention further comprises:
(C) purging system, comprising:
(C1) inert blowing gas sweeping device 202, is connected to the second end of the second sampling pipeline 16 by the 5th pipeline;
(C2) the 5th valve 5, is arranged on the 5th pipeline.
Preferably, catalyst slurry acquisition system of the present invention further comprises:
(D) slurry reactor system, it comprises: the reaction product discharging pipeline 15 that unstripped gas injects pipeline 13, stirred tank reactor 8, still internal filter 9 and is attached thereto.
In Fig. 1 alphabetical A by arrow mark the liquid level in stirred tank reactor 8.
As shown in Figure 1, a kind of system of fischer-tropsch synthetic catalyst evaluating apparatus online acquisition catalyst slurry comprises:
Liquid wax injected system: liquid wax accumulator tanks 1, liquid wax injection pump 2, liquid wax inject the 6th valve (stop valve) 3, the 4th valve (ball valve) 4 and tensimeter 17 on the 4th pipeline 12 and the 4th pipeline 12, the first sampling pipeline 14 with and on the first valve (ball valve) 6 (also using this pipeline and valve while gathering still inner catalyst slurries);
Stirred tank reactive system: unstripped gas injected system 13, stirred tank reactor 8, still internal filter 9 and with it reaction product discharging pipeline 15;
Catalyst slurry acquisition system: the first sampling pipeline 14 and on the 5th valve (ball valve) 5 and the first valve (ball valve) 6, the second sampling pipeline 16 and on second valve (ball valve) 7, the 3rd valve (stop valve) 10 and tensimeter 18, slurries holding tank 11.
Preferably, unstripped gas is synthetic gas (CO and H
2) or pure H
2, pure CO, gas agent is than for 1000-10000ml/g-cat./h.
Preferably, the concentration of stirred tank inner catalyst slurries is 2-20wt%.
Preferably, when stirred tank inner catalyst reduces or reacts, temperature is 200-300 ℃.
Preferably, when stirred tank inner catalyst reduces or reacts, pressure is 0.5-3.0MPa.
Preferably, the mode of collection catalyst slurry is batch (-type).
Preferably, the pipeline in catalyst slurry acquisition system and valve all add electric tracing, and companion's hot temperature degree is 100-200 ℃.
Preferably, catalyst slurry holding tank is resistant to elevated temperatures stainless steel or glass container.
Preferably, in catalyzer sampling system, pipeline and valve all have certain abrasion resistance.
Preferably, in catalyzer sampling pipeline reactor, the internal diameter of part and the internal diameter of the outer part of still are identical or different.
Further illustrate the working method of patent supplying method of the present invention below in conjunction with accompanying drawing 1, but the present invention is not therefore subject to any restriction.
One preferred embodiment in, the method for sampling of the present invention, is divided into three steps: sampling prepare, sampling, sampling after cleaning and purging.
(a ') sampling preparation
1, confirm whether the electric tracing temperature on sampling the first sampling pipeline 14 and 16 reaches normal design temperature;
2,, by drawing temperature (assaying reaction temperature in the kettle) to determine, the interior liquid level of reactor 8, higher than sampling the first sampling pipeline 14 lower port, at built-in filter lower end, guarantees that liquid level is higher than the about 20mm of the first sampling pipeline 14 lower port; If liquid level is lower, start pump 2, close the 5th valve 5, the first valve 6 and second valve 7, after pump discharge pressure table 17 shows that pressure is higher than the about 0.5MPa of reactor 8, open the first valve 6, to injection liquid wax in reactor, until liquid level reaches requirement in still.
In the sampling preparatory stage, the preparation of sampling instrument, protective gloves, safety goggles and slurries holding tank etc. need to be ready to before sampling.
(a) sampling
(1) common, sampling needs two operator's compounding practices, people's nurse, people's sampling;
(2) open the first valve 6 and second valve 7, close the 3rd valve 10, catalyst slurry in reactor is entered in the first sampling pipeline 14 and 16, in the time that tensimeter 18 shows that pressure is identical with reacting kettle inner pressure, close second valve 7, slowly open the 3rd valve 10, catalyst slurry is collected in serum pot 11;
(3) repeat aforesaid operations 2-3 time, collect after required slurries, close the first valve 6, open second valve 7 and the 3rd valve 10.
(c) clean and (d) purge
(1) start pump 2, open valve 3,4,7,10, to sampling pipeline 14,16 in filling liquid paraffin, clean;
(2) after cleaning up, termination of pumping 2, shut-off valve 4, connects and purges low pressure N from the 5th valve 5
2, sampling pipeline is purged to approximately 5 minutes;
(3) after purging, close the 5th valve 5 and the 3rd valve 10.
This system is the catalyst slurry in online acquisition paste state bed reactor easily.
Embodiment
In this embodiment, be the applicable cases of method provided by the present invention in syrup state bed Fischer Tropsch synthesis iron base catalyst R&D work.
SFT418 fischer-tropsch synthetic catalyst and a certain amount of whiteruss 35g to Shenhua Group pack into after slurry reactor still 8, reductase 12 4 hours under the condition of 250 ℃, 0.5MPa, pure hydrogen atmosphere (gas agent is than being 2000ml/g-cat./h), after reduction finishes, switch under the condition of 265 ℃, 2.3MPa, synthetic gas (hydrogen-carbon ratio is 1.5, and gas agent is than being 2000ml/g-cat./h) and react 500h.Wherein at when reduction, reaction 100h, 200h, gather catalyst slurry at 300 o'clock.Sampling when reduction and in course of reaction is slightly had any different.
1. the slurries collection in reduction process
Owing to not producing liquid wax product in reduction process, liquid level when reduction finishes in reactor may, lower than sampling pipeline 6 lower port, need to be injected a certain amount of whiteruss in still.Concrete steps are as follows:
(1) confirm that the electric tracing temperature on sampling the first sampling pipeline 14 and 16 reaches 150 ℃ of normal design temperatures;
(2) by drawing temperature (assaying reaction temperature in the kettle) to determine, the interior liquid level of reactor 8 is lower than the about 10mm of the first sampling pipeline 14 lower port; Start pump 2, close the 5th valve 5, the first valve 6 and second valve 7, after pump discharge pressure table 17 shows that pressure is higher than the about 0.5MPa of reactor 8, open the first valve 6, to injection liquid wax in reactor, after the about 200g of injection liquid wax, the first valve 6 is closed in termination of pumping 2 simultaneously;
(3) again draw temperature (assaying reaction temperature in the kettle), after confirming that the interior liquid level of reactor 8 is higher than the about 20mm of the first sampling pipeline 14 lower port, open the first valve 6 and second valve 7, close the 3rd valve 10, catalyst slurry in reactor is entered in pipeline 14 and 16, in the time that tensimeter 18 shows that pressure is identical with reacting kettle inner pressure, close second valve 7, slowly open the 3rd valve 10, catalyst slurry is collected in serum pot 11;
(4) repeat above-mentioned 3) operate 2-3 time, collect after about 60g slurries, close the first valve 6, open second valve 7 and the 3rd valve 10.
(5) start pump 2, open valve 3,4,7,10, to sampling pipeline in filling liquid paraffin, clean;
(6) after cleaning up, termination of pumping 2, shut-off valve 4, connects and purges low pressure N from the 5th valve 5
2, sampling pipeline is purged to approximately 5 minutes;
(7) after purging, close the 5th valve 5 and the 3rd valve 10.
2. the catalyst slurry collection in course of reaction
In fischer-tropsch reaction process, produce product liquid, the interior liquid level of reactor 8 is higher than the first sampling pipeline 14 lower port, do not need to filling liquid paraffin in still, and concrete sampling step is as follows:
(1) confirm that the electric tracing temperature on the first sampling pipeline 14 and 16 reaches 150 ℃ of normal design temperatures;
(2) by drawing temperature (assaying reaction temperature in the kettle) to determine, the interior liquid level of reactor 8 is higher than the about 20mm of the first sampling pipeline 14 lower port;
(3) open the first valve 6 and second valve 7, close the 3rd valve 10, catalyst slurry in reactor is entered in pipeline 14 and 16, in the time that tensimeter 18 shows that pressure is identical with reacting kettle inner pressure, close second valve 7, slowly open the 3rd valve 10, catalyst slurry is collected in serum pot 11;
(4) repeat above-mentioned 3) operate 2-3 time, collect after about 60g slurries, close the first valve 6, open second valve 7 and the 3rd valve 10.
(5) start pump 2, open valve 3,4,7,10, to sampling pipeline in filling liquid paraffin, clean;
(6) after cleaning up, termination of pumping 2, shut-off valve 4, connects and purges low pressure N from the 5th valve 5
2, sampling pipeline is purged to approximately 5 minutes;
(7) after purging, close the 5th valve 5 and the 3rd valve 10.
3. the property analysis of catalyzer in slurries
By the catalyzer gathering out, after dimethylbenzene extracting, then carry out sreen analysis by Ma Erwen 2000 particle size distribution analysis instrument, the granularity in differential responses stage is in table 1.
The sreen analysis of table 1 different phase catalyzer
Note: D50 refers to while making particle size distribution analysis, and the catalyst granules granularity of 50% volume is at this more than value;
50 microns of <, refer to that granularity is less than the percent by volume of the catalyst granules of 50 microns.
Certainly, the present invention also can have other embodiments, these are only the preferred embodiment of the present invention, is not used for limiting protection scope of the present invention; Without departing from the spirit of the invention, those of ordinary skills are every makes various corresponding variations and modification according to content of the present invention, all belongs to the protection domain of claim of the present invention.
Claims (19)
1. a catalyst slurry on-line acquisition system, wherein said catalyst slurry is contained in paste state bed reactor (8), comprising:
(A) sampling system, comprising:
(A1) the first sampling pipeline (14), has first end and the second end, and the first end of described the first sampling pipeline (14) extend in paste state bed reactor (8), wherein, is provided with the first valve (6) on the first sampling pipeline;
(A2) the second sampling pipeline (16), has first end and the second end, and the second end of described the second sampling pipeline (16) is connected to the second end of described the first sampling pipeline (14); Wherein, be provided with second valve (7) at the second end place of described the second sampling pipeline (16), the first end place of described the second sampling pipeline (16) is provided with the 3rd valve (10);
(A3) catalyst slurry collection container (11), be connected to described second sampling pipeline (16) first end;
(A4) pressure monitoring device (18), is connected on described the second sampling pipeline (16) between described second valve (7) and described the 3rd valve (10) by the 3rd pipeline, and described pressure monitoring device (18) is tensimeter;
(B) inert media injected system, comprising:
(B1) inertia liquid medium feeding mechanism (1); With
(B2) the 4th pipeline (12), is connected to the second end of described the first sampling pipeline (14) and the second end of described the second sampling pipeline (16) by described inertia liquid medium feeding mechanism (1), is provided with the 4th valve (4) on wherein said the 4th pipeline.
2. catalyst slurry on-line acquisition system according to claim 1, wherein, is provided with U-shaped pipe in described the 3rd pipeline, fills inertia liquid medium in U-shaped pipe.
3. catalyst slurry on-line acquisition system according to claim 1, wherein, described (B) inert media injected system further comprises:
(B3) pump (2), is arranged between described the 4th valve (4) and described inertia liquid medium feeding mechanism (1).
4. catalyst slurry on-line acquisition system according to claim 3, wherein, described (B) inert media injected system further comprises:
(B4) pressure monitoring device (17), is arranged between described pump (2) and described the 4th valve (4).
5. catalyst slurry on-line acquisition system according to claim 1, further comprises:
(C) purging system, comprising:
(C1) inert blowing gas sweeping device (202), by the 5th pipeline be connected to described second sampling pipeline (16) the second end;
(C2) the 5th valve (5), is arranged on described the 5th pipeline.
6. catalyst slurry on-line acquisition system according to claim 1, wherein, pipeline and valve in described (A) sampling system are wear-resistant pipeline and wear-resisting valve.
7. catalyst slurry on-line acquisition system according to claim 4, wherein, the described pressure monitoring device (18) in described pressure monitoring device (17) and described (A) sampling system in described (B) inert media injected system is tensimeter.
8. catalyst slurry on-line acquisition system according to claim 1, in described (A) sampling system, described (B) inert media injected system, outer pipeline and the valve of paste state bed reactor (8) is provided with heating arrangement or heating device.
9. according to the catalyst slurry on-line acquisition system described in claim 1 to 8 any one, wherein, described paste state bed reactor (8) is Fischer-Tropsch synthetic pulp state bed reactor (8); Described inertia liquid medium feeding mechanism (1) is liquid wax feeding mechanism (1).
10. a catalyst slurry online acquisition method, by carrying out according to the system described in claim 1 to 9 any one, the method comprises:
(a) close described the 3rd valve (10), open described the first valve (6) and described second valve (7), make the catalyst slurry in described paste state bed reactor (8) enter described (A1) first sampling pipeline (14) and described (A2) second sampling pipeline (16);
(b) close described second valve (7), open described the 3rd valve (10), described catalyst slurry is collected in described (A3) catalyst slurry collection container (11).
11. methods according to claim 10, wherein, described inertia liquid medium is identical with reaction medium or product in described paste state bed reactor (8).
12. methods according to claim 10, wherein, the pressure in described paste state bed reactor (8) is greater than external environment condition pressure.
13. methods according to claim 10, wherein, in described paste state bed reactor (8), temperature is 200～320 ℃.
14. methods according to claim 10, wherein, further comprise: in step (a) before,
(a ') by described (B) inert media injected system, inert media is injected in described paste state bed reactor (8) until interior the liquid level of described paste state bed reactor (8) higher than the described first first end preset distance H that samples pipeline (14).
15. methods according to claim 10, wherein, in the time that described system has heating arrangement or heating device, the heating-up temperature of described heating arrangement or heating device or companion's hot temperature degree are 100～200 ℃.
16. methods according to claim 10, further comprise:
(d) cleaning step: inject inertia liquid medium by described (B) inert media injected system in described the first sampling pipeline (14) and described the second sampling pipeline (16), clean.
17. methods according to claim 10, wherein, in the time that described catalyst slurry on-line acquisition system comprises (C) purging system, the method further comprises:
(e) purge step: described the second sampling pipeline (16) is purged by purging system.
18. methods according to claim 10, wherein, the mode that gathers catalyst slurry is batch (-type).
19. according to claim 10 to the method described in 18 any one, and wherein, described catalyst slurry online acquisition method is the catalyst slurry online acquisition method in fischer-tropsch synthetic catalyst reduction phase or Fischer-Tropsch synthesis stage.
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| CN102854038A (en) * | 2012-10-09 | 2013-01-02 | 力合科技（湖南）股份有限公司 | Sampling system for process analysis |
| CN107860613B (en) * | 2017-10-16 | 2020-10-02 | 湖北三江航天江河化工科技有限公司 | Safe sampling device of nitrate adhesive |
| CN108732294B (en) * | 2018-05-31 | 2021-06-29 | 中石化（洛阳）科技有限公司 | On-line reaction performance evaluation system for catalyst of moving bed device, reaction performance evaluation method thereof and moving bed device |
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