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CN1301794C - Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process - Google Patents

Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process Download PDF

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CN1301794C
CN1301794C CNB2004100416189A CN200410041618A CN1301794C CN 1301794 C CN1301794 C CN 1301794C CN B2004100416189 A CNB2004100416189 A CN B2004100416189A CN 200410041618 A CN200410041618 A CN 200410041618A CN 1301794 C CN1301794 C CN 1301794C
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catalyst
yield
molecular sieve
zeolite
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CN1597112A (en
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董家禄
张伟峰
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Abstract

The present invention discloses a molecular sieve type catalyst for preparing low carbon olefine by the catalyzing thermal cracking process. The catalyst is a composite catalyst comprising acidic zeolite with high silicon and aluminum ratio, and the oxide of a second component, or a composite catalyst formed by that an acidic zeolite with the high silicon and aluminum ratio, and oxide containing transition metal are loaded on an alkali zeolite with high silicon and aluminum ratio. The two composite catalysts are called the molecular sieve catalyst. The present invention proposes 7 specific realization schemes. The present invention has the advantages that the reaction temperature is from 620 to 690 DEG C, preferably 680 DEG C or so, the reaction temperature is lower than the reaction temperature (750 to 800DEG. C) reported by a document or a patent, the total yield of the olefine with C2 to C4 is high, the total yield is 15 to 30% higher than a value reported by the document or the patent at the temperature of 680 to 690 DEG C, and the olefine with the C2 to the C4 comprises most of the C2 and the C4, wherein C2 content is from 24% to 37%, and C3 content is from 11% to 36%.

Description

A kind of molecular sieve type catalyst of catalytic pyrolysis producing light olefins
One, technical field
The present invention relates to a kind of catalyst, specifically is a kind of molecular sieve type catalyst by n-hexane, light oil, naphtha and decompression diesel oil catalytic thermal cracking process to prepare lower olefine, and especially a kind of being applicable to produced the catalyst that is rich in ethene.
Two, background technology
Ethene is one of important foundation raw material in the chemical industry, is the important symbol of weighing a national petrochemical industry level.Be to be raw material at present, adopt the method for thermal cracking to produce ethene with hydro carbons (as naphtha etc.).This method is generally carried out under 830～870 ℃, often adopt raising method of temperature (＞850～950 ℃) for improving yield of ethene, but energy consumption height, investment is big, equipment requires harsh, crude oil quality variation day by day in recent years particularly, and heavy oil fraction proportion increases, cause olefin yields to reduce, coke and jelly increase.In order to improve particularly yield of ethene of olefin yields, reduce cracking temperature, alleviate huge energy consumption and investment, relatively Shi Yi method is to introduce catalyst in hot tearing process (Catalytic pyrolysis) or be called TCSC process (Thermo-Catalytic Steam Cracking Process).Adopt this process can reduce reaction temperature, and the heavy oil fraction need not directly to obtain through any preliminary treatment the low-carbon alkene of high yield.Catalyst (comprising co-catalyst) is introduced the TCSC process, and its purpose is: (1) reduces reaction temperature, reduces energy consumption; (2) improve cracking reaction speed; (3) improve the selectivity and the yield of pyrolysis product, improve the flexibility that product distributes; (4) provide the technology of can processing heavy hydrocarbon class fraction producing alkene.Up to the present, there is the three major types material to can be used as the catalyst of this process in the work few in number that patent documentation is reported: (1) silicate and zeolite crystal thereof; (2) alkali metal/alkali earth metal aluminate; (3) various carriers are (as zeolite, float stone, Al 2O 3Deng) upward metal oxide-loaded.Н e Ф т e х М й и я 30 (4), 486, (1990), 19 (4), 601, (1979), 18 (2), 237, (1978), Ж. φ. Х .58 (11), 2839, (1984) and U.S.Pat.3647682 (1972), U.S.Pat.3644557 (1972) has reported М, у, Ц В М type and ultra high silicon type zeolite research light oil, butane, the catalytic cracking of gas-oil, show reaction temperature under 550～650 ℃, olefin yields reaches as high as at 51% o'clock in gas, and yield of ethene is up to 30～40% of gas gross, compare with thermal cracking, reaction temperature descends more than 175 ℃, but carbon deposit is serious, and catalyst life is short; Н e Φ т e х и М и я 18,237, (1978), 18,577, (1979), U.S.Pat.3644557 (1972), Ger.Pat.2340904 (1974), U.S.Pat.3872179 (1975) and U.S.Pat.4087350 (1978) have reported and have utilized MgO, ZrO 2, MnO 2Make active constituent, add metal/alkaline-earth metal at Al 2O 3, HfO 2Make catalyst on the carrier, make raw material with residual oil, naphtha, n-hexane etc., reaction temperature at 700～750 ℃ of following yield of ethene 36～41%; Н e Φ т e х и М и я 31 (5), 668, (1991), 18 (2), 237, (1978), U.S.Pat.3767567 (1973), Eur.Pat.Appl.0262049A2 (1988) and U.S.S.R.1298240 (1987) have reported and have utilized KVO 3/ Al 2O 3, In 2O 3/ Al 2O 3, K 2SnO 3/ Al 2O 3, CaOAl 2O 3Mix with any material among BaO, MgO or the SrO, or with HZSM-5, catalyst researches such as Zn-Mn-HZSM-5 the cracking process of raw material such as alkane compound such as n-hexane and gasoline, naphtha, yield of ethene reaches as high as 43.9% in 700～800 ℃ of following gases; China Guangdong petrochemical industry junior college has also carried out the exploration of system ethene, and research is pointed out on the fluid bed better to the residual oil cracking effect with the molecular sieve alumina silicate catalyst, and the triolefin yield can reach 48～50%; China Petroleum Chemicals Corporation utilizes HZSM-5 to mix the catalyst of forming with y-type zeolite, produce low-carbon alkene especially propylene and butylene, its patent No. is CN1043520A, in CN1083092A, CN1221015, then utilize the lamellar clay molecular sieve/or the acidic molecular sieve that contains the five-membered ring silica-rich zeolite of rare earth make Catalyst Production ethene and propylene, its yield of ethene is respectively 20% (700 ℃) and 21% (700 ℃), and the triolefin yield is respectively 50% and 54%.In CN1222558A, then make Catalyst Production ethene and propylene with the acidic molecular sieve of the five-membered ring silica-rich zeolite of modification Y type and modification, with the vacuum gas oil (VGO) be raw material under 680 ℃ of reactions, the ethene yield only is 20%, the triolefin yield is 54%, and carbon distribution is up to more than 9%.
In sum, the temperature of catalytic cracking is 680～800 ℃ at present, suitable temperature is 680～750 ℃, though the temperature than thermal cracking has reduced by 50～100 ℃, but reaction temperature is still quite high, this has brought many difficulties to technology, and in the existing catalyst be best with the oxide, but difficulty is bigger in preparation process, even in CN1317543, adopts the zeolite-loaded Ag/Cu of ZSM-5 type to make the Catalyst Production low-carbon alkene, its reaction temperature is 650-680 ℃, the employing light diesel fuel is a raw material, but yield of ethene only is 12.52%, and the alkatrienes yield only is 39.51%; Adopting the five-membered ring silica-rich zeolite of layer column molecular sieve and modification to make catalyst among the CN1218786, is raw material with the light diesel fuel, and under 650 °-750 ℃, it only is 18% that ethene adds propene yield.Therefore studying suitable efficient cryogenic catalyst is still a significant problem.
Three, summary of the invention
The objective of the invention is at the deficiencies in the prior art, the molecular sieve type catalyst of the catalytic cracking producing light olefins that a kind of reaction temperature is low, carbon distribution is few, catalyst life is long, olefin yields is high is provided.
Technical scheme of the present invention is: a kind of molecular sieve type catalyst of catalytic cracking producing light olefins is characterized in that it is the Ce on NaM or the KM of loading on of the acid zeolite HZSM-5 of 30%-70% and 30%-70% by weight 2O 3Form.
The composite catalyst that constitutes with the oxide of the acid zeolite of high silica alumina ratio and second component, or the acid zeolite of high silica alumina ratio loads on the composite catalyst that constitutes on the another kind of basic zeolite than high silica alumina ratio with containing transition metal oxide, is referred to as molecular sieve catalyst.
Be that the composite catalyst that the oxide of the acid zeolite HZSM-5 of 35%-65% and 35%-65% constitutes is formed specifically by weight; Be that the acid zeolite HZSM-5 of 30%-70% and the transition metal oxide that contains of 30%-70% are carried on the composite catalyst that constitutes on NaM or the KM perhaps by weight; Or form by the acid zeolite HZSM-5 of weight 35%-65% and the KM of 35-65%.
Described oxide is MoO 3, or contain Fe 2O 3, Cu 2O, CaO, K 2The mixture of O or contain α-Fe 2O 3And Cr 2O 3Mixture or contain Cr 2O 3And Al 2O 3Mixture;
Described transition metal oxide is Ce 2O 3
The acid zeolite of high silica alumina ratio is a HZSM-5 type zeolite, and its silica alumina ratio is greater than 35, and the optimum 40-60 of being (presses SiO 2/ Al 2O 3Meter).
Described HZSM-5 type zeolite can be the synthetic NaZSM-5 type zeolite of no amine, is h-type zeolite again after ion-exchange, also can be with organic amine or the synthetic ZSM-5 type zeolite of inorganic amine, also can be the total silicon zeolite.
Described oxide is the composite oxides that contain elements such as Fe, Cr, Mo, Cu, V, Ca, K, Al, Si, wherein with Cr 2O 3-Al 2O 3The oxide optimum that constitutes.
Describedly contain the oxide that transition metal oxide comprises elements such as Mo, Pb, La, Ce, basic zeolite is NaM or KM type zeolite, wherein with Ce 2O 3Load on KM and go up optimum.
The described molecular sieve type catalyst that is made of the oxide of the acid zeolite and second component, the two can the mixed pressuring plate moulding, also can distinguish compression molding, mixes it again.
The cracking process of hydro carbons under superheated vapor on the catalyst is that the catalytic cracking process that is taken place on the thermal cracking of gas phase part and the catalyst surface carries out simultaneously.
When using the molecular sieve type catalyst of high silica alumina ratio, reaction temperature is lower, and has the effect of water-fast steam.The present invention selects to have for example HZSM-5 and oxide with dehydrogenation or the load composite catalyst that has the basic zeolite of transition metal to mix mutually of acid zeolite that suitable acid-base value and acid measures, wherein HZSM-5 type zeolite accounts for 35～65%, and second component accounts for 65～35%.
ZSM-5 type zeolite is preferably selected SiO 2/ Al 2O 3Than the HZSM-5 that is 35～100, optimum SiO 2/ Al 2O 3Than 40～60, ZSM-5 type zeolite can be synthetic with organic amine, also can be inorganic amine or not have amine synthetic, and optimum is the ZSM-5 type zeolite that adopts quaternary amine synthetic.If adopt the synthetic ZSM-5 type zeolite of no amine, then need use NH 4Cl or NH 4NO 3The aqueous solution is exchanged into HZSM-5 type zeolite.
If second component adopts transition metal oxide to be carried on the basic zeolite, then can adopt Mo, Pb, La, Ce salt, as sodium molybdate, amine molybdate, plumbi nitras, lanthanum nitrate, strontium nitrate, can be corresponding chlorinated lanthanum, strontium nitrate etc. also, be carried on NaM or KM or the NaKM.
If second component adopts oxide, can adopt the oxide of elements such as containing Fe, Cr, Mo, Cu, V, Ca, K, Al, Si or the salt of hydride or corresponding metal element, the for example nitrate of copper, iron, chromium or chloride, amine molybdate, potassium molybdate, potassium hydroxide calcination and get, aluminium can adopt Al 2O 3, Al 2O 3NH 2The salt of O or aluminium such as aluminum nitrate, aluminium chloride.
The invention provides the method for preparing catalyst and have following two kinds:
Method (1): a) with the calcination of ZSM-5 type zeolite/or ion-exchange after calcination again/or both have concurrently and make HZSM-5 type zeolite, b) if the second component oxide is then made composite oxides with the method for co-precipitation according to a certain ratio, if support type zeolite, can be on alkaline modenite with the chloride of coherent element or the full dip loading of nitrate, drying gets Me after the roasting 2O/NaM (or KM); C) with a), b) mix the back compression molding mutually according to a certain ratio.
Method (2): a) b) compression molding respectively mutually is contained in the reactor by a certain percentage with above-mentioned, and its order is that a) the gained compressing tablet is placed on b) the gained compressing tablet above.
Catalyst provided by the invention has following advantage in order to produce low-carbon alkene: (1) reaction temperature is 620～690 ℃, and optimum is about 680 ℃, be lower than the reaction temperature of document or patent report; (2) C = 2Yield and C 2～C 4The alkene total recovery is higher, all exceeds 10-20% than document or patent report value in the time of 680～690 ℃; (3) C 2～C 4C in the alkene 2, C 4Account for the overwhelming majority, wherein C 2Account for 24～37%, C 3Account for 11～36%.
Four, the specific embodiment
Below will the invention will be further described by embodiment.
Embodiment 1: the synthetic ZSM-5 type zeolite of 10 gram organic amines is placed Muffle furnace, flow down roasting at oxygen or air, oxygen gas flow rate is 20mlmin -1Or air velocity is 30mlmin -1, sintering temperature is 600 ℃, and roasting time is 6 hours (carrying out under oxygen or air atmosphere), and compression molding is made two kinds of catalyst A and B then.
The synthetic NaZSM-5 type zeolite of the no amine of 10 grams is placed three-necked bottle, add 5.4 gram NH 4CL (C.P.) adds 100 gram water again, stirs, and exchange was clarified after 1 hour when being warmed up to 90 ℃, and the solution that inclines adds 5.4 gram NH again 4CL, 100 gram water continue to heat up, and stir, and exchange 1 hour under 90 ℃ again, exchange so repeatedly totally 6 times, and subsequent filtration, 0.1%AgNO is used in washing again 3After solution is checked through no Cl-1, dry under 100 ℃, 600 ℃ of following roastings 6 hours (under oxygen or air atmosphere, carrying out), cooling, compression molding is made catalyst C.
Embodiment 2: the catalytic pyrolysis that carries out n-hexane in the small fixed reactor assembly reacts catalyst A, B, the C that is used for estimating among the embodiment 1, and its reaction condition and reaction result are listed table 1 in.With the synthetic ZSM-5 type zeolite of organic amine, the HZSM-5 type zeolite that is labeled as A is best as can be seen from Table 1, and its conversion ratio is up to 82.4%, and the carbon deposit minimum is 0.4%, and wherein the triolefin yield is 62%, C 2Be 22%; Compare the performance of the catalytic pyrolysis of catalyst A, B, C, by finding out in the table 1 that the hexane conversion rate is by A＞C＞B＞blank pipe, the triolefin yield is by A＞C＞B＞blank pipe, wherein C 2Yield is by A＞C＞B＞blank pipe, C 3Yield is the order reduction by A＞C＞B＞blank pipe, and as seen that a kind of HZSM-5 type zeolite is that thermal cracking is much better than blank pipe all.
Table 1
Raw material N-hexane N-hexane N-hexane N-hexane
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) A 3.61 0.90 0.50 60 617 82.4 83.4 2.6 7.6 22.0 7.1 37.3 0 2.7 2.7 1.3 0.1 0.4 16.2 1.70 62.0 B 3.61 0.90 0.50 60 617 77.8 79.0 2.4 12.1 16.4 7.3 24.7 0 6.5 6.0 3.5 0.1 0.7 20.3 1.51 47.6 C 3.61 0.90 0.50 60 617 67.3 67.7 1.1 8.1 18.1 6.5 29.0 0 1.8 2.8 0 0.3 0.5 31.8 1.60 48.9 Blank pipe 3.61 0.90 0.50 60 617 30.6 30.1 0 4.2 10.7 1.6 8.7 0 3.9 0 0.5 0.5 0 69.9 0.81 23.3
Embodiment 3: with the powder and the Al of catalyst B among the embodiment 1 2O 3H 2O evenly mixes in 65: 35 ratio, compressing tablet behind the mixing, and the 10-20 order that sieves 600 ℃ of following roastings 4 hours, is made catalyst D.
Embodiment 4: the device of pressing embodiment 2 is measured the catalytic activity that catalyst D goes up hexane, naphtha, light diesel fuel, decompression diesel oil catalytic pyrolysis, and its reaction condition and reaction result are listed table 2 in.(1) as can be seen from Table 2, the total olefin yield of n-hexane is than DNAcarrier free catalyst B height, particularly C 3 =Alkene has increased by 10 percentage points, and coke is reduced to from 0.7% and is almost 0, so adds carrier in the zeolite, not only can not reduce catalytic activity, and help reducing the generation of coke. and gas recovery ratio was more when (2) naphtha was raw material, C 3 =More, its total olefin yield is greater than 60%.
Table 2
Raw material N-hexane Naphtha Light diesel fuel Decompression diesel oil
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) D 3.6 0.90 0.50 60 617 84.6 85.4 2.0 10.6 18.6 8.3 34.2 0 3.7 4.5 1.4 2.1 0 14.6 1.84 56.5 D 2.62 0.76 0.60 60 652 - 89.4 1.4 14.6 27.3 7.3 23.0 0.4 11.5 1.4 1.1 1.4 3.0 7.6 0.84 61.8 D 3.30 0.61 0.60 60 691 - 76.0 1.5 16.3 25.8 5.8 12.7 2.2 9.2 0.2 1.4 0.9 5.4 18.6 0.49 47.7 D 2.85 0.60 0.70 40 682 - 78.3 1.2 18.6 24.8 7.1 10.5 0.2 12.3 1.1 0.9 1.6 10.4 11.3 0.42 47.6
Embodiment 5: 1.33 gram amine molybdates are dissolved in the 20ml water, pour 9 gram NaM into, water-bath under agitation is heated to about 80 ℃, remains on below 80 ℃ to stir, and is evaporated to driedly, and note is made e.Catalyst A powder among e and the embodiment 1 is evenly mixed in 30: 70 ratio, stir evenly the back compressing tablet, the 10-20 order that sieves, (carry out under air atmosphere, air velocity was 30mlmin 600 ℃ of following roastings 6 hours -1), note is made catalyst E.
Embodiment 6: carry out catalytic pyrolysis and react the catalyst E that estimates among the embodiment 5 in the device of embodiment 2, its reaction condition and reaction result are as shown in table 3.(1) as can be seen from Table 3, the conversion ratio that catalyst E goes up n-hexane improves 10% than on catalyst A, wherein C 2 =, C 4 =Alkene all has increase in various degree.(2) light diesel fuel/decompression diesel oil the high 2-3 of gas recovery ratio percentage point on catalyst E than on D, C 2 =1 percentage point of corresponding increase is respectively 26.7% and 25.5%, and total olefin increases 3-4 percentage point, and the few 45-65% of carbon deposit on the catalyst.
Table 3
Raw material N-hexane Light diesel fuel Decompression diesel oil
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) E 3.61 0.90 0.50 60 617 90.3 90.6 2.4 9.5 24.3 7.2 32.2 0 8.1 5.9 0.7 0.3 0.8 8.6 1.33 64.6 E 3.16 0.63 0.61 60 689 - 78.9 1.2 16.8 26.7 5.3 13.2 2.1 11.2 1.3 0.3 0.8 1.9 19.2 0.49 51.1 E 2.79 0.61 0.70 40 679 - 80.0 1.0 17.1 25.5 6.2 11.8 0.2 14.8 1.3 1.0 1.1 5.7 14.3 0.46 52.1
Embodiment 7: with 0.80 gram Ce (NO 3) 36H 2O is soluble in water fully, under agitation adds 9.7 gram NaM or KM, and water-bath under agitation is heated to about 80 ℃ then, remains on 80 ℃ and stirs down, is evaporated to driedly, and note is made f.F is evenly mixed in 30: 70 ratio with the catalyst A among the embodiment 1, stir evenly the back compressing tablet, the 10-20 order that sieves, 600 ℃ of following roastings 6 hours, note was made catalyst F-1 (NaM) and F-2 (KM).
Embodiment 8: carry out catalytic pyrolysis and react catalyst F-1 and the F-2 that estimates among the embodiment 7 in the device of embodiment 2, its reaction condition and reaction result are as shown in table 4.(1) as can be seen from Table 4, n-hexane is being urged
Table 4
Raw material N-hexane Naphtha Light diesel fuel
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) F-1 3.61 0.90 0.50 60 617 87.3 86.9 2.2 8.2 23.7 7.0 35.5 0 4.2 5.9 0 0.2 0.4 12.7 1.5 63.4 F-2 2.51 0.80 0.60 54 681 - 90.4 1.4 20.4 31.4 5.6 17.5 1.5 9.5 1.1 0.9 1.1 1.1 8.5 0.56 58.4 F-2 3.14 0.64 0.60 60 685 - 73.8 1.1 17.4 26.2 6.1 13.2 1.8 5.3 1.1 0.8 0.8 2.2 24.0 0.5 44.7
The conversion ratio of changing on the agent F-1 has improved 6% than on catalyst A, total olefin yield and C 2Yield all increases to some extent, and the carbon deposit performance is only about the same with catalyst A.When (2) naphtha was raw material, yield of ethene reached 31.4% on catalyst F-2, and total olefin reaches 58.4%, and coke content is all lower than catalyst D, E.
Embodiment 9: take by weighing 2.3 gram F (NO 3) 39H 2O puts into beaker a, adds water and makes its lucky dissolving, under agitation drips 1: 1 ammonia spirit, and Fe (OH) is arranged this moment 3Precipitation occurs, and continues dropping ammonia solution after precipitation no longer increases, and adds 3 ammonia spirits again.Simultaneously with 1.34 gram Cu (NO 3) 2.3H 2O puts into beaker b, adds water
Table 5
Raw material N-hexane N-hexane
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) G 3.61 0.90 0.50 60 677 97.5 96.7 3.2 23.9 35.1 7.1 22.6 0 4.0 0 0.3 0.5 1.3 2.0 0.64 61.7 Blank pipe 3.61 0.90 0.50 60 677 60.3 58.7 0 8.8 24.7 2.1 15.3 0 7.6 00 0.2 0.2 41.1 0.62 47.6
Make its lucky dissolving, under constantly stirring with the b beaker in solution pour in a beaker, under agitation add 7.18 gram CaO powder after stirring evenly, mix the back 200 ℃ dry down, grind to form fine powder then, add 3.07 gram K again 2CO 3, fully mixing the back 600 ℃ of following roastings 6 hours, note is made g.G is evenly mixed in 35: 65 ratio with the catalyst A among the embodiment 1, stir evenly the back compressing tablet, the 10-20 order that sieves, 600 ℃ of following roastings 6 hours, note was made catalyst G.
G is evenly mixed in 65: 35 ratio with the catalyst A among the embodiment 1, stir evenly the back compressing tablet, the 10-20 order that sieves, 600 ℃ of following roastings 6 hours, note was made catalyst H.
Table 6
Raw material N-hexane Light diesel fuel
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) H 3.61 0.90 0.50 60 677 92.1 92.0 1.2 16.6 32.9 4.5 18.5 0 17.9 0 0 0.4 0.6 7.4 0.56 69.3 H 3.26 0.61 0.60 60 687 76.8 1.6 16.5 23.7 5.7 11.7 1.7 10.9 0.8 1.3 2.9 5.2 18.0 0.49 46.3
Embodiment 10: carry out catalytic cracking and react catalyst G and the H that estimates among the embodiment 9 in the device of embodiment 2, its reaction condition and reaction result are respectively shown in table 5 and table 6.From table 5 and table 6 as can be seen, hexane total olefin yield on catalyst G and H exceeds 30% and 46% than blank pipe respectively, wherein C 2 =+ C 3 =Exceed 44% and 29% than blank pipe respectively on yield catalyst G and H, catalyst G goes up C 2Yield is up to 35.1%, and catalyst H goes up C 4The yield increase is obvious especially, and its yield is 17.9%, and only is 4.0% on the catalyst G, this shows to regulate the distribution that catalyst A and the second component ratio can be regulated product.
Embodiment 11: take by weighing 3.9 gram K 2CO 3Be dissolved in the 10ml water, add 9 gram α-Fe then 2O 3After stirring evenly, add 0.375 gram Cr again 2O 3Continue to stir evenly, under stirring evenly, be heated to about 90 ℃, remain on 90 ℃ and stir down, be evaporated to dried.Then 200 ℃ of oven dry down.Behind the porphyrize, 600 ℃ of following roastings 6 hours, note was made i.I is evenly mixed in 35: 65 ratio with the catalyst A among the embodiment 1, stir evenly the back compressing tablet, the 10-20 order that sieves, 600 ℃ of following roastings 6 hours, note was made catalyst I.
I is evenly mixed in 65: 35 ratio with the catalyst A among the embodiment 1, stir evenly the back compressing tablet, the 10-20 order that sieves, 600 ℃ of following roastings 6 hours, note was made catalyst J.
Embodiment 12: carry out catalytic pyrolysis and react I and the J that estimates among the embodiment 11 in the device of embodiment 2, its reaction condition and reaction result are listed table 7 and table 8 respectively in.(1) from table 7 and table 8 as can be seen, n-hexane is C on J 2Yield will exceed 50% up to 37.1% than blank pipe, and total olefin exceeds 46% up to 69.4% than blank pipe, and carbon distribution and not serious.N-hexane is C on catalyst I 2Reach the total olefin yield and exceed 28% and 38% than blank pipe respectively, wherein C 5Increase very greatly, yield is 1.4%.This shows, regulate the ratio of A and second component [Fe-Cr-k] and can control the product distribution effectively, to improve C 2 =The yield of alkene.When (2) as can be seen from Table 7, being raw material with decompression diesel oil on catalyst I C 2 =And the total olefin yield is suitable with catalyst E, but carbon deposition quantity lacks 46% than E.(3) as can be seen from Table 8, no matter which kind of oil product is a raw material, and carbon deposition quantity is all very low on catalyst J, and gas recovery ratio is not second to other catalyst.The C when diesel oil that wherein reduces pressure is raw material 2Yield is up to 26.1%.
Embodiment 13: with 3.95 gram Cr (NO 3) 39H 2O is dissolved in the 60 gram water, and water-bath is heated to about 85 ℃, under agitation uses 1: 1 ammonia spirit to drip in system, has this moment precipitation to occur, and continuing dropping ammonia solution is 10-11 up to the PH of system.Continue to stir 5min down at 85 ℃ then, filter, drying is 2 hours under 100 ℃, 300 ℃ of roasting half an hour, be warming up to 500 insulations and be warming up to 600 ℃ of insulations 3 hours after 1 hour again, continue to be warming up to 700 ℃ of insulation half an hour then, be warmed up to 800 ℃ of insulations 5 hours at last, cooling is ground, and note is made k.K is evenly mixed in 35: 65 ratio with the catalyst A among the embodiment 1, stir evenly the back compressing tablet, the 10-20 order that sieves, 600 times roastings 6 hours, note was made catalyst K.
Embodiment 14: carry out catalytic pyrolysis and react the catalyst K that estimates among the embodiment 13 in the device of embodiment 2, its reaction condition and reaction result are listed table 9 in.(1) as can be seen from Table 9, n-hexane total olefin yield on catalyst K compare with blank pipe increase more, C particularly wherein 4, its yield reaches 15.3%.(2) as can be seen from Table 9, with naphtha, light diesel fuel, C when decompression diesel oil is raw material on catalyst K 2Yield reaches 31.5%, 28.6%, 26.9%, is higher than other several catalyst far away.
Table 7
Raw material N-hexane N-hexane Light diesel fuel Decompression diesel oil
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) I 3.61 0.90 0.50 60 677 91.1 89.5 1.7 16.1 31.5 4.7 21.7 0 12.3 0 1.4 0.1 2.3 8.2 0.69 65.5 I 2.69 0.74 0.60 60 683 89.1 0.8 17.7 28.0 5.0 18.5 0.9 14.1 3.3 0.3 0.5 1.0 9.9 0.66 60.6 I 3.23 0.62 0.60 60 684 76.1 0.8 16.1 25.5 5.9 14.5 1.4 9.9 1.6 0.2 0.2 2.2 21.7 0.57 49.9 I 2.69 0.58 0.70 40 683 78.0 0.6 16.5 25.6 6.1 12.6 0.1 13.4 1.8 0.7 0.6 3.1 18.9 0.49 51.6
Table 8
Raw material N-hexane Naphtha Decompression diesel oil
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) J 3.61 0.90 0.50 60 677 87.0 86.3 0.9 12.9 37.1 2.8 22.5 0 9.8 0 0 0.3 0.6 13.1 0.61 69.1 J 2.68 0.75 0.60 60 685 88.7 0.9 19.9 28.5 5.7 15.9 1.8 10.7 3.6 1.1 0.6 0.3 11.0 0.56 55.1 J 2.78 0.62 0.70 40 684 77.9 0.5 17.8 26.1 6.7 12.5 0.1 11.2 1.4 0.8 0.8 1.6 20.5 0.48 49.8
Implement loudspeaker 15: the f (KM) among the i among the embodiment 11, the embodiment 7 is evenly mixed in 32.5: 15: 52.5 ratio with the catalyst A among the embodiment 1, stir evenly the back compressing tablet, the 10-20 order that sieves, 600 ℃ of following roastings 6 hours, note was made catalyst L.
Embodiment 16: carry out catalytic cracking and react the catalyst L that estimates among the embodiment 15 in the device of embodiment 2, its reaction condition and reaction result are as shown in table 10.(1) catalyst L is actually the combination of catalyst I and F-2.(2) as can be seen from Table 10, C when being raw material with naphtha 4Obviously increase, total olefin improves 2 percentage points than catalyst F-2, so the composition of regulating catalyst according to demand.(3) it can also be seen that C when being raw material with decompression diesel oil from table 10 2Yield is up to 26.6%.
Table 9
Raw material N-hexane Naphtha Light diesel fuel Decompression diesel oil
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) conversion ratio (wt%) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) K 3.61 0.90 0.50 60 677 84.7 1.1 12.2 29.5 3.7 22.7 0 15.3 0 0 0.2 0.8 14.5 0.77 67.5 K 2.57 0.78 0.60 60 686 89.3 1.3 19.6 31.5 6.1 17.9 1.7 8.5 1.6 0.0 1.1 2.7 8.0 0.57 57.9 K 3.18 0.63 0.60 60 691 76.3 1.1 18.5 28.6 5.9 12.6 1.3 6.2 0.1 1.1 0.9 1.1 22.6 0.44 47.4 K 3.16 0.54 0.70 40 682 82.1 0.7 12.9 26.9 4.8 16.8 0.2 15.0 1.8 1.6 1.4 3.2 14.7 0.62 58.7
Embodiment 17: adopt the catalyst F-2 among the embodiment 7 to carry out the catalytic pyrolysis reaction of naphtha in the device of embodiment 2, do a contrast with the industrial crack data of same naphtha, concrete reaction condition and reaction result are listed table 11 in.As can be seen from Table 11, the catalyst F-2 of this patent is higher 7 percentage points than industrial hot pyrolysis gas yield, C 3, C 4Yield obviously improves, and exceeds 26% and 45% respectively, but reaction temperature obviously reduces by 152 ℃.
Table 10
Raw material Naphtha Decompression diesel oil
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) L 2.56 0.78 0.60 60 682 90.1 0.8 17.5 27.6 4.9 17.3 1.8 15.5 3.8 0.3 0.6 1.1 8.8 0.63 60.4 L 2.82 0.61 0.70 40 679 78.4 0.6 17.0 26.6 6.3 12.8 0.1 12.5 0.8 1.0 0.7 3.0 18.6 0.48 51.9
Table 11
Reaction unit Small fixed Commercial plant
Catalyst raw material air speed WHSV (hr -1) the water hydrocarbon than (wt%) catalytic amount (g) reaction time (min) reaction temperature (℃) product yield (wt%) gas H wherein2 CH 4 C 2H 4 C 2H 6 C 3H 6 C 3H 8 C 4 ＝ C 4 C 5C is at CO XMiddle solid C liquid C in catalyst 3H 6/C 2H 4Total olefin amount (wt%) F-2 2.64 0.76 0.60 60 678 93.4 1.0 20.8 27.1 6.4 19.4 0.1 15.1 0.9 1.8 1.0 0.4 6.2 0.71 61.4 - - - - - 830 85.4 1.1 16.9 27.0 3.8 15.2 0.7 10.4 0.3 9.8 0.2 14.6 0.56 52.6
Subordinate list 1 naphtha group composition (PONA)
Carbon number N-alkane Isoparaffin Cycloalkane Aromatic hydrocarbon
3 0.00 0.00 0.00 0.00
4 0.16 0.00 0.00 0.00
5 5.30 3.16 1.43 0.00
6 6.85 16.24 4.40 0.61
7 6.33 4.19 6.51 1.40
8 6.04 6.74 5.78 3.54
9 4.45 2.07 6.38 1.40
10 0.91 3.24 1.40 0.33
11 0.18 0.68 0.00 0.03
12 0.04 0.22 0.00 0.00
Add up to 30.28 36.53 25.89 7.30
The rare Material Characteristics parameter of subordinate list 2 second
Raw material Naphtha Light diesel fuel Decompression diesel oil
Characterization factor K 12.25 10.12 10.52
Density (20 ℃) g/cm 3 0.706 0.813 0.855
Correlation index BMCI 8.6 18.6 16.8
C/Hratio 5.59 7.19 7.03
Hydrogen content (wt%) 15.2 11.6 12.1
The boiling range of subordinate list 3 naphthas
Boiling range ℃
Initial boiling point 39.0
10％/30％ 58.5/75.0
50％/70％ 94.0/118.5
90％/95％ 146.0/162.0
100％ 191.0
The boiling range of subordinate list 4 light diesel fuels
Boiling range ℃
Initial boiling point 180
10％/20％ 204/221
30％/40％ 236/250
50％/60％ 264/277
70％/80％ 293/308
90％/93％ 332/350
Boiling range and other parameter of subordinate list 5 decompression diesel oil
Refractive power n 20 D 1.4771
Sulphur ppm 727
Nitrogen ppm 528
Carbon residue m% 0.02
Boiling range (D-1160) ℃
Initial boiling point/10% 227/368
20％/30％ 385/403
50％/70％ 436/467
90％/95％ 507/524
The naphtha group composition (PONA) of subordinate list 6 commercial plants
Carbon number Alkane Cycloalkane Aromatic hydrocarbon
3 0.00 0.00
4 (C3-5)5.56 0.00 0.00
5 2.36 0.00
6 36.50 11.94 0.27
7 23.35 8.17 0.69
8 4.70 4.52 0.29
9 0.96 0.40 0.02
10 0.21 0.03 0.00
11-12 0.03 0.00 0.00
Add up to 71.31 27.42 1.27

Claims (1)

1, a kind of molecular sieve type catalyst of catalytic cracking producing light olefins, it is characterized in that it by weight be the acid zeolite HZSM-5 of 30%-70% and 30%-70% load Ce 2O 3NaM or KM form.
CNB2004100416189A 2004-08-06 2004-08-06 Molecular sieve type catalyst of low carbon olefine by catalizing thermo cracking process Expired - Fee Related CN1301794C (en)

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CN104475151A (en) * 2014-12-11 2015-04-01 郭帅 Novel efficient environment-friendly catalyst for regeneration of used oil
CN112940770A (en) * 2021-02-20 2021-06-11 东南大学 Device and method for directional depolymerization and conversion of biomass into aviation oil cycloparaffin component

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US4418235A (en) * 1980-02-14 1983-11-29 Mobil Oil Corporation Hydrocarbon conversion with zeolite having enhanced catalytic activity
US4719004A (en) * 1982-06-23 1988-01-12 Mobil Oil Corporation Cracking/dewaxing with high silica zeolite mulled with water and binder
US4912275A (en) * 1987-08-05 1990-03-27 Mobil Oil Corporation Ammonium activation of zeolites in the presence of gaseous ammonia
CN1043520A (en) * 1988-12-21 1990-07-04 中国石油化工总公司石油化工科学研究院 A kind of catalyst for cracking of producing low-carbon alkene
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