CN1093734A

CN1093734A - Method for preparation of catalyst cracking combustion-supporting agent

Info

Publication number: CN1093734A
Application number: CN 93104262
Authority: CN
Inventors: 陈禄; 卢立军
Original assignee: Sinopec Research Institute of Petroleum Processing
Current assignee: Sinopec Research Institute of Petroleum Processing
Priority date: 1993-04-15
Filing date: 1993-04-15
Publication date: 1994-10-19
Anticipated expiration: 2013-04-15
Also published as: CN1034222C

Abstract

A kind of preparation method who is used for the noble-metal load type ignition dope is a raw material with the useless agent residue behind the platiniferous spent catalyst recovery precious metal, makes through steps such as pulverizing, screening, chemical modification processing, drying and roastings.The active ingredient of ignition dope is a platinum, and content is 0.005-0.05%.The technology of producing ignition dope with present method is simple, and cost is low.The carbon monoxide activity of conversion height of ignition dope, the hydrothermally stable performance is good.

Description

Method for preparation of catalyst cracking combustion-supporting agent

The invention relates to the preparation method of ignition dope used in the petroleum refining catalytic cracking process, or rather, the present invention is to be the method that raw material is produced the catalytic cracking CO (carbon monoxide converter) combustion promoter with the residue of platiniferous spent catalyst after reclaiming platinum.

Catalytic cracking is the technological process of most important a kind of heavy oil lighting in the refinery.In catalytic cracking process, catalyzer makes mink cell focus be cracked into gas and lightweight oil in reactor, simultaneously because of its active significantly reduction of deposit carbon on catalyzer.For the cracking activity that recovers catalyzer and supply with required heat, the catalyzer of deposit carbon just is sent to after reaction and removes to burn carbon in the revivifier, emits carbonic acid gas (CO when burning carbon ₂) and carbon monoxide (CO)." after-burning " phenomenon can take place in CO, is damaged with the construction and device that causes catalyzer, and has polluted environment because of the atmosphere that drains into of CO.In order to address this problem, the U.S. has at first used the technology of CO ignition dope in catalytic cracking unit in 1975, the many-sides such as yield that it pollutes, improves operation, recovered energy and raising lightweight oil in the activity that improves cracking catalyst, raising regeneration temperature, the carbon content that reduces regenerator, minimizing all have significant improvement, thereby make the application of CO ignition dope obtain development rapidly.

Mostly the active component of CO ignition dope is the precious metal of VIII family, and the most frequently used is platinum (Pt) and palladium (Pd).The adding mode of ignition dope has several: a kind of is that the oil soluble salt of precious metal is joined in the catalytically cracked stock, or the water-soluble salt of precious metal be injected in the catalytic cracking process in the water vapor that must add; Another kind is the precious metal that makes the cracking catalyst load 20～80ppm of small portion; Also having a kind of is the molecular sieve supported cracking catalyst that contains precious metal of making on carrier that contains precious metal; Last a kind of be noble metal support on inorganic oxide as ignition dope, separate use with catalytic cracking catalyst, as US 4,214,978.China adopts last a kind of load that the aluminum oxide of precious metal or the ignition dope of other inorganic oxides are arranged, and separates with catalytic cracking catalyst and uses to reduce the consumption of precious metal.As CN 87106173.2 Pt or Pd are loaded on the aluminum oxide that contains metal or contain the aluminum oxide of metal and the mixture of other inorganic oxides on, make the CO ignition dope.CN 1049301A is with Pt or Pd loads on cracking catalyst or its matrix reaches by Al ₂O ₃-Re ₂O ₃-ZrO ₃CO ignition dope on the carrier of forming.The ignition dope of loading type is under the operational condition of high-temperature water vapor, and the platinum of its load easily condenses and reduces combustion-supporting activity, need constantly add new ignition dope.The expense that this not only will increase ignition dope also will consume expensive platinum.Though the price of palladium is lower than platinum, but the ignition dope activity that contains palladium also is lower than the platiniferous ignition dope, the content of palladium in ignition dope is also much higher than platinum, in device, the reserve of palladium is bigger more than five times than platinum, in a word, the ignition dope that directly uses precious metals preparations such as platinum, palladium more than on cost all than higher.

In recent years because developing rapidly of organic synthesis, oil refining and petrochemical industry contains the also constantly increase of catalyst levels of platinum family precious metal.The catalyzer that contains the platinum family precious metal generally all will recycle precious metal through the useless agent behind the life-time service, so that reuse contained precious metal.The technology that also has many precious metals to reclaim is delivered both at home and abroad, but after reaching the desired rate of recovery, disposes for still containing the very low useless agent residue of noble metal amount discarded way then commonly used, and this has just not only wasted precious metal, and environment is polluted.

Because the low levels residue during the useless agent of the needs of above-mentioned catalyst cracking combustion-supporting agent and precious metal is reclaimed fails to utilize problem, it is raw material that purpose of the present invention will propose with this residue exactly, prepares the method for CO ignition dope.

The inventive method is that residue is pulverized, sieved, again through promptly making platiniferous CO ignition dope after chemical modification processing, drying, the roasting.

The platiniferous spent catalyst of the inventive method indication is monometallic or the many metals spent catalyst that contains platinum.Its carrier is aluminum oxide or the mixture or the miscellany of aluminum oxide and silicon oxide.Owing on the platiniferous spent catalyst carbon distribution is arranged, when reclaiming platinum, all extract platinum, but carrier keeps through the roasting de-carbon and with mineral acid.Generally be lower than 0.05% through the platinum content in the residue behind the recovery platinum.

Chemical modification is handled the hydrothermal stability that helps to improve CO oxidation activity and ignition dope.It is to carry out with reference to the introducing metallic salt technology among the CN87106173.2 that the chemical modification of the inventive method is handled.Used metal-salt has copper (Cu), magnesium (Mg), zinc (Zn), tin (Sn), titanium (Ti), cobalt (Co), nickel (Ni) etc. to comprise water soluble salts such as muriate, nitrate, acetate.The aqueous solution with wherein one or more metal-salts flooded 8～24 hours at normal temperatures, 120 ℃ of dryings 2～5 hours, then 350～800 ℃ of roastings 1～5 hour, was preferably in 600～800 ℃ of roastings 1～4 hour again, promptly made finished product CO ignition dope.Because the platinum content difference in the raw material residue, the platinum content in finished product CO ignition dope can scope 0.005～0.10% in, preferably 0.005～0.05%.As the metal content (in oxide compound) of chemical modification is 0.2～10.0%, preferably 0.2～5.0%.

With existing ignition dope preparation method relatively the time, the inventive method is with through reclaiming catalyst residue behind the platinum as the preparation raw material, and therefore with low cost, the process of preparation is also fairly simple.The ignition dope of preparing has CO activity of conversion height, the premium properties of good hydrothermal stability.Use the inventive method both to have improved the use of platinum, also reduced the pollution of residue environment all be that the residue of discarding is utilized again in the past.

Below be the embodiment of the inventive method.

Embodiment 1-5

With the residue that useless platinum-Xi reforming catalyst process reclaims behind the platinum is raw material, prepares the CO ignition dope according to the inventive method.With platinum content is that 0.01% residue is pulverized, and sieves into the particulate that granularity is 80～300 sieve meshes.Take by weighing the Mg(NO of 0.13 gram, 0.64 gram, 1.93 grams, 3.21 grams and 6.42 grams respectively ₃) ₂6H ₂Is produced from the O(Beijing Chemical Plant, chemical pure), become solution with an amount of dissolved in distilled water.Take by weighing 5 parts of above-mentioned residues again, every part heavy 10 gram.Join Mg(NO respectively ₃) ₂Solution in, stir.At room temperature flooded 12 hours, then 120 ℃ of dryings after 2 hours again 700 ℃ of roastings 3 hours, promptly make the CO ignition dope.

The above CO ignition dope that makes is measured active on the small fixed flowing bed-tion reacting device of laboratory.The adding carbon deposition quantity is industrial rare earth-Y zeolite cracking catalyst 30 gram and an amount of ignition dopes of 1.1～1.2% in device, and making the reserve of platinum in device is 0.4ppm.Under nitrogen protection, heat up; making revivifier dense-phase bed temperature is 600 ℃; the dilute phase bed temperature is 370～380 ℃; switching air then begins catalyst regeneration; the intake air gauge pressure is 0.05MPa; air flow quantity is 1.0 liters/minute, measures the gas composition of regenerated flue gas and calculates the oxidation activity of CO ignition dope, with the CO in the regenerated flue gas ₂With the ratio of CO content as oxidation activity, the results are shown in Table 1.

Table 1

Embodiment	Platinum content	Metal oxide (MgO) content, %	Oxidation activity (CO ₂/CO)
					Fresh dose	Aging agent (800 ℃, 4 hours)
			1 2 3 4 5	0.01 0.01 0.01 0.01 0.01			0.2 1.0 3.0 5.0 10.0	70.77 51.11 58.67 40.43 29.67	58.50 35.79 52.94 36.54 26.82

Embodiment 6-11

With the residue that useless platinum-Xi reforming catalyst process reclaims behind the platinum is raw material, prepares the CO ignition dope according to the inventive method.With platinum content is that 0.01% residue is pulverized, and sieves the particle into granularity 80～300 sieve meshes.Get various metal-salts (being the chemically pure reagent that the Beijing Chemical Plant produces) by following weight fraction another name:

Ni(CH ₃COO) ₂4H ₂O 0.34 gram

Co(CH ₃COO) ₂4H ₂O 0.34 gram

TiCl ₃Solution (contains TiCl ₃20%) 0.97 gram

Zn(NO ₃) ₂6H ₂O 0.37 gram

6 parts of above-mentioned metal-salts earlier with an amount of dissolved in distilled water, are taken by weighing 6 parts of useless agent residues again, every part of each 10 gram, add in the aqueous solution of metal-salt, stir, at room temperature flooded 8 hours, after 2 hours, press the temperature and time roasting in the table 2 120 ℃ of dryings then, promptly make the CO ignition dope.According to the oxidation activity of embodiment 1-5 same operation step measurements CO ignition dope, the results are shown in Table 2.

Table 2

Embodiment

Platinum content %

Metal oxide

Roasting condition

Chlorization activity (CO ₂/CO)

Title

Content %

Temperature ℃

Time hour

Fresh dose

800 ℃ of aging agent 4 hours

6 7 8 9 10 11

0.01 0.01 0.01 0.01 0.01 0.01

NiO CoO TiO ₂ZnO NiO CoO MgO TiO ₂

1 1 1 1 0.5 0.5 0.5 0.5

800 750 600 800 700 800

1 2 5 1 3 1

58.67 58.13 62.00 62.00 66.15 70.00

35.38 41.30 38.69 21.63 47.22 45.26

Embodiment 12-14

With the residue behind useless reforming Pt-Re catalyst process recovery platinum and the rhenium is raw material, prepares the CO ignition dope according to the inventive method.Because the platinum content difference in the used former spent catalyst, the platinum content in the residue is respectively 0.005%, 0.03% and 0.05%.Residue is pulverized, after screening is 80～300 granularities, taken by weighing Mg(NO according to the amount in the table 3 ₃) ₂6H ₂O is with an amount of dissolved in distilled water.Take by weighing each 10 gram of residue, add in the corresponding magnesium nitrate solution, after stirring, at room temperature flooded 8 hours, again in 120 ℃ dry 3 hours down, stirred 3 hours down at 600 ℃, promptly make the CO ignition dope.The mensuration of its oxidation activity is identical with embodiment 1-5, the results are shown in Table 3.

Table 3

Embodiment	Platinum content %	Mg(NO ₃) ₂·6H ₂The O gram	MgO content %	Oxidation activity (CO ₂/CO）
						Fresh dose	800 ℃ of aging agent, 4 hours
				12 13 14	0.005 0.03 0.05			0.32 0.64 0.64	0.5 1.0 1.0	54.21 35.82 45.20	50.50 21.52 27.64

Embodiment 15

Present embodiment is the comparative example of the CO ignition dope performance of the inventive method preparation.According to the method for CN 87106173.2, take by weighing 0.39 gram Mg(CH ₃COO) ₂6H ₂O 0.39 gram (Beijing Chemical Plant, chemical pure) is dissolved in an amount of distilled water.Get an amount of microballoon α-gibbsite (Zhengzhou Aluminium Plant's Industrial products), measure its burn decrement rate of 850 ℃.Take by weighing a certain amount of aluminum oxide precursor microballoon according to this burn decrement rate, make it be equivalent to 850 ℃ of aluminum oxide 10 grams after the igloss.Be immersed in the hole saturation method in the solution of magnesium acetate, then 115 ℃ of dryings 6 hours, 900 ℃ of roastings 4 hours promptly make content of magnesia and are 1.1% the magnesium-alumina supporter that contains.With its load platinum, make the CO ignition dope of platiniferous 0.02% with the pickling process of routine.With embodiment 1-5 identical operations condition under measure fresh dose of this ignition dope oxidation activity be that 41.06,800 ℃ of aging agent oxidation activities of 4 hours are 25.00.

Claims

1, a kind of be used for petroleum catalytic cracking processing be active ingredient with the precious metal and be the load-carbon oxide accelerator preparation method of carrier with the inorganic oxide, it is characterized in that with the useless agent residue behind the platiniferous spent catalyst recovery platinum be raw material, make through steps such as pulverizing, screening, chemical modification processing, drying and roastings.

2, according to the ignition dope preparation method of claim 1, the active component that it is characterized in that said platiniferous spent catalyst is platiniferous monometallic or many metals, and carrier is aluminum oxide or the mixture or the mixture of aluminum oxide and silicon oxide.

3, according to the ignition dope preparation method of claim 1, it is characterized in that said useless agent residue is the residue after platiniferous spent catalyst process reclaims platinum, residue has kept the carrier of raw catalyst, and the platinum content of residue is lower than 0.05%.

4, according to the ignition dope preparation method of claim 1, it is characterized in that it is that the solution of one or more water soluble salts in the muriate, nitrate, acetate with copper, magnesium, zinc, tin, titanium, cobalt, nickel flooded 8～24 hours at normal temperatures that said chemical modification is handled, 120 ℃ of dryings 2～5 hours, 350～800 ℃ of roastings 1～5 hour, be preferably in 600～800 ℃ of roastings 1～4 hour, the metal content of chemical modification (in oxide compound) is 0.2～10.0%, is preferably 0.2～5.0%.

5,, it is characterized in that the platinum content of the ignition dope that makes is 0.005～0.05% according to the ignition dope preparation method of claim 1.