CN102600826A - Catalytic cracking assistant composition and catalytic cracking assistant - Google Patents

Abstract

The invention provides a catalytic cracking assistant composition which can reduce coke yield in catalytic cracking, comprising following components based on total weight of the catalytic cracking assistant composition: 2-65wt% of silicon-magnesium adhesive, 1-25wt% of rare-earth compound and 15-85wt% of monohydrate bauxite. The invention also provides a catalytic cracking assistant which can reduce coke yield in catalytic cracking is obtained by spray drying, granulating and roasting the catalytic cracking assistant composition and water after being beaten. In the catalytic cracking assistant provided by the invention, due to the silicon-magnesium adhesive, the rare-earth compound and the monohydrate bauxite as materials, the catalytic cracking assistant has large matrix specific surface area, proper acidity and excellent heavy oil conversion capability, notably improves absorption rate of gasoline and diesel and notably reduces yield of coke and dry gas.

Description

A kind of catalytic cracking additive composition and catalytic cracking additive

technical field

The present invention relates to a kind of catalytic cracking auxiliary agent composition and the catalytic cracking auxiliary agent prepared by the composition, more specifically to a kind of catalytic cracking auxiliary agent composition which reduces the yield of catalytic cracking coke and the composition Catalytic cracking additives made from products.

Background technique

Reducing carbon dioxide emissions is a consensus reached by governments around the world. Our government has promised to reduce carbon emissions per unit of GDP by 40% in 2020. According to statistics, in 2002, the carbon dioxide emissions produced by the US oil refining industry accounted for 20% of the total carbon dioxide emissions produced by the US industry in the same year, while the carbon dioxide emissions produced by catalytic cracking ranked first in the oil refining industry, accounting for 15-20% of the refinery carbon dioxide emissions. 30%. Therefore, to reduce refinery carbon dioxide emissions must first reduce catalytic cracking carbon dioxide emissions. Carbon dioxide emissions from catalytic cracking are mainly generated during catalyst regeneration and coking. Therefore, reducing carbon dioxide emissions from catalytic cracking must reduce the coke yield of catalytic cracking.

Reducing the yield of catalytic cracking coke not only has great social benefits, but also has huge economic benefits, especially after the carbon dioxide emission tax is imposed in the near future, reducing the yield of catalytic cracking coke will be the common task of all refineries.

There are five types of catalytic cracking coke: agent-oil ratio coke, polluted coke, catalytic coke, feed coke and thermal cracking coke. Catalyst oil specific coke is coke produced by residual hydrocarbons entering the regenerator after stripping; polluted coke is coke produced by the reaction caused by polluted metals and their activity; catalytic coke comes from catalytic cracking reactions, including unimolecular reaction process and bimolecular reaction process; feed The coke comes from the raw material Kang's residual carbon; the thermal cracking coke is the raw coke from the thermal cracking reaction.

Traditional catalytic cracking catalysts that reduce coke yields mostly use ultra-stable molecular sieves and inert substrates to reduce catalysts. Report a kind of modified molecular sieve that can improve coking as CN101537366A, and its unit cell parameter is

Intercat Company reported a heavy oil conversion aid (BCA-105) in patent WO9712011, which is characterized in containing three kinds of alumina, one of which is pseudo-boehmite, and the other is silicon-containing pseudo-boehmite structure Aluminum hydroxide, the third is insoluble aluminum hydroxide, BCA-105 does not contain rare earth, nor does it contain magnesium oxide.

CN101745373A reports a catalytic cracking additive, which is characterized in that it contains two kinds of alumina with stepped pore distribution, one is macroporous alumina and the other is small pore alumina. CN1978593B has reported a kind of catalytic cracking catalyst, it is characterized in that catalyst contains a kind of mesoporous material with pseudo-boehmite structure, and this mesoporous material contains aluminum oxide, silicon oxide and metal oxide, such as magnesium oxide or rare earth oxide wait. CN1322917C reports a mesoporous silicon-aluminum material and a preparation method thereof. All of the aluminum in the mesoporous silicon-aluminum material is four-coordinated. CN1964785A reports a kind of FCC method using mesoporous catalyst, this mesoporous catalyst does not contain The holes, the mesopores are concentrated in

Contents of the invention

The object of the present invention is to provide a catalytic cracking aid composition and a catalytic cracking aid capable of reducing the yield of catalytic cracking coke.

The invention provides a catalytic cracking additive composition capable of reducing the yield of catalytic cracking coke. Based on the total weight of the catalytic cracking additive composition, the catalytic cracking additive composition contains 2 to 65% by weight of silica-magnesia gel , 1-25% by weight of rare earth compounds, 25-85% by weight of gibbsite.

The present invention also provides a catalytic cracking aid capable of reducing the yield of catalytic cracking coke. The catalytic cracking aid is prepared by beating the catalytic cracking aid composition with water, spray drying, granulating and roasting.

The catalytic cracking additive provided by the present invention uses silica-magnesia gel, rare earth compound and gibbsite as raw materials, so it has a large matrix specific surface area, can greatly increase the yield of catalytic cracking coke, and has excellent heavy oil conversion ability. As can be seen from the data in the following examples, when the catalytic cracking additive of the present invention is used in conjunction with the catalytic balancer for heavy oil conversion, the output of coke and dry gas is significantly reduced, while the total yield of liquefied gas, gasoline and diesel oil is significantly improved. For example, when adopting the catalytic cracking aid of embodiment 2, the yield of dry gas and coke is respectively 2.5% and 6.8%, and the total yield of liquefied gas, gasoline and diesel oil is 87.6%; And under the same situation of other conditions , the dry gas and coke yields were 3.2% and 8.6% respectively when the imported in-situ crystallization coagent was used, and the total yield of liquefied gas, gasoline and diesel oil was 85.2%. The coke yield of the former is 1.8% lower than that of the latter, and the total yield of liquefied gas, gasoline and diesel is increased by 2.4%.

Detailed ways

The invention provides a catalytic cracking additive composition capable of reducing the yield of catalytic cracking coke, based on the total weight of the catalytic cracking additive composition, and on a dry basis, the catalytic cracking additive composition contains 2 to 65 % by weight silica-magnesia gel, 1-25% by weight of rare earth compound, 25-85% by weight of gibbsite.

In the catalytic cracking aid composition provided by the present invention, the silica-magnesium colloid is a substance similar to silica-alumina colloid known in the art, and is a colloidal particle with a large specific surface area. It can be prepared by methods known to those skilled in the art, for example, it can be prepared according to the method of US Patent No. 3,129,189.

Based on the weight of silicon-magnesium glue, in terms of dry weight and in terms of oxides, the content of magnesium oxide in the silicon-magnesium glue can be 10 to 40% by weight, preferably 15 to 30% by weight; The content may be 60-90% by weight, preferably 67.5-84% by weight; the content of fluorine element may be 0-3% by weight, preferably 0.1-2.5% by weight.

The rare earth compound may be various rare earth compounds known to those skilled in the art, and the rare earth compound is preferably one or more of rare earth oxides, rare earth hydroxides, rare earth nitrates and rare earth carbonates. The rare earth element in the rare earth compound is one of lanthanum, cerium, samarium, praseodymium, neodymium, promethium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactium, uranium and neptunium One or more, preferably one or more of lanthanum, cerium and samarium.

The boehmite includes one or more of various boehmite and diaspore known to those skilled in the art, preferably boehmite, more preferably pseudo-boehmite and/or or boehmite.

The shape of the boehmite is not particularly required, and is preferably flake and/or fibrous. The shape of the boehmite described here may be flake-like and/or fibrous, which means that all of the boehmite may be flake-like, all of the boehmite may be fibrous, or a part may be flake-like, and the other part may be It is fibrous. The thickness of the flakes may be 5 nm-100 nm, the length of the fibers may be 10-200 nm, and the diameter may be 2 nm-50 nm.

Preferably, the catalytic cracking additive composition provided by the present invention may also contain 0-5% by weight of MFI shape-selective molecular sieve and 2-10% by weight of binder based on the total amount of the catalytic cracking additive composition and 0 to 60% by weight of clay. According to one embodiment of the present invention, based on the total weight of the catalytic cracking additive composition, the composition contains 5-20% by weight of silica-magnesium gel, 1-10% by weight of rare earth oxide, 15-65% by weight The gibbsite, 0-5% by weight of MFI shape-selective molecular sieve, 2-10% by weight of binder and 20-60% by weight of clay. Preferably, based on the total weight of the catalytic cracking additive composition, the composition contains 8-15% by weight of silica-magnesia gel, 2-5% by weight of rare earth oxides, and 30-45% by weight of gibbsite , 0-5% by weight of MFI shape-selective molecular sieve, 3-9% by weight of binder and 40-55% by weight of clay.

The MFI structure shape-selective molecular sieve may be an MFI structure-selective molecular sieve known to those skilled in the art, preferably a ZSM-5 molecular sieve.

The clay is selected from clays commonly used in cracking catalysts and additives, for example, the clay can be selected from one of kaolin, halloysite, sepiolite, diatomaceous earth, retortite, attapulgite, bentonite and montmorillonite species or several.

The binder can be selected from binders commonly used in catalytic cracking additives, such as one or more of aluminum sol, silica sol, silica-alumina sol, hydrated alumina and their precursors, preferably aluminum One or more of colloidal sol, silica sol, and silica-alumina sol.

The preparation method of the catalytic cracking additive composition capable of reducing the yield of catalytic cracking coke provided by the present invention is simple, and only needs to mix the corresponding components uniformly.

The present invention also provides a catalytic cracking aid capable of reducing the yield of catalytic cracking coke. The catalytic cracking aid is prepared from the above catalytic cracking aid composition provided by the present invention and water, and then subjected to spray drying, granulation and roasting.

The amount of the water used is not particularly limited, as long as the catalytic cracking aid composition can form a uniform slurry. Preferably, the weight ratio of the catalytic cracking additive composition to water is 1:1-10, preferably 1:1.5-5.

The spray-drying granulation can be carried out using various spray-drying equipment known in the art. Preferably, the temperature of the spray-drying tail gas during the spray-drying and granulation is 100-150°C.

The calcination method is a conventional method in the art, the calcination temperature is preferably 450-650°C, and the calcination time is preferably 0.2-5 hours, more preferably 0.5-2 hours.

According to the present invention, the preparation method of the catalytic cracking aid that can reduce the yield of catalytic cracking coke includes making the above catalytic cracking aid composition provided by the present invention and water, followed by spray drying, granulation and roasting in one go. The various components of the above-mentioned catalytic cracking auxiliary composition can be mixed uniformly first, and then mixed with water for beating after obtaining the mixture, or the various components of the above-mentioned catalytic cracking auxiliary composition can be directly mixed with water alone or together without pre-mixing Mix for beating. The amount of water used, spray-drying granulation and roasting have been described above and will not be repeated here.

The following examples will further illustrate the present invention, but the protection scope of the present invention is not limited by these examples. In the following examples, the wear index is a straight pipe method, measured by the Q/SH 3360208-2006 standard. The heap ratio is measured according to the Q/SH 3360 207-2006 standard test method.

Example 1

According to U.S. Patent No. 3129189, prepare fluorine-containing silica-magnesia gel, in the obtained silica-magnesia gel, the content of magnesium oxide is 28.0% by weight, and the content of silicon dioxide is 69.4% by weight based on the dry basis weight of silica-magnesia gel. %, the content of sodium oxide is 0.1% by weight; the content of fluorine element is 2.5% by weight, and the BET specific surface area of the silica-magnesia gel is 526m ² /g, and the pore volume is 0.52ml/g.

Add 2000 grams of water in the reaction kettle, and then add 60 grams of silicon-magnesium colloid (by dry basis weight, the same below), 27 grams of lanthanum oxide, and 18 grams of aluminum sol (produced by Jianchang Branch of Sinopec Catalyst Company) under vigorous stirring. , the content of alumina is 21.0% by weight, the addition is by weight on a dry basis, the same below), 225 grams of pseudo-boehmite (produced by Shanxi Aluminum Factory, the content of alumina is 60.0% by weight, and the addition is by weight on a dry basis total, the same below) and 270 grams of halloysite (produced by Hunan Chenxi Tianyuan Company, the water content is 29.1% by weight, and the addition is based on dry weight, the same below), after stirring for 30 minutes, it was spray-dried and granulated, and the tail gas was spray-dried The temperature is 105°C, and then calcined at 550°C for 30 minutes to obtain catalytic cracking aid A.

The BET specific surface area of catalytic cracking additive A is 165m ² /g, the wear index is 1.1, and the heap ratio is 0.72g/ml.

Example 2

According to U.S. Patent No. 3,129,189, prepare fluorine-containing silica-magnesia gel. In the obtained silica-magnesia gel, the content of magnesium oxide is 16.0% by weight, and the content of silicon dioxide is 81.9% based on the dry weight of silica-magnesia gel and in terms of oxides. % by weight, the content of sodium oxide is 0.1% by weight; the content of fluorine element is 2.0% by weight, and the BET specific surface area of the silica-magnesia gel is 512m ² /g, and the pore volume is 0.65ml/g.

Add 2400 grams of water in the reactor, then add 90 grams of magnesium silica gel successively under vigorous stirring, 30 grams of lanthanum carbonate, 54 grams of aluminum sol, 186 grams of fibrous boehmite (provided by Aluminum Corporation of China, fiber diameter is 8 nanometers, length is 100 nanometers, pore volume 1.1ml/g, add-on is by dry basis weight) and 240 grams of kaolin (produced by Suzhou Kaolin Company, water content is 30.0% by weight, add-on is by dry basis weight, the following same), stirring for 30 minutes and then spray drying, the temperature of the spray drying tail gas is 120°C, and then roasted at 450°C for 2 hours to obtain catalytic cracking additive B.

The BET specific surface area of catalytic cracking aid B is 182m ² /g, the wear index is 1.6, and the heap ratio is 0.68g/ml.

Example 3

According to U.S. Patent No. 3,129,189, prepare fluorine-containing silica-magnesia gel. In the obtained silica-magnesia gel, the content of magnesium oxide is 28.0% by weight, and the content of silicon dioxide is 69.4% by weight based on the dry weight of silica-magnesia gel. % by weight, the content of sodium oxide is 0.1% by weight; the content of fluorine element is 2.5% by weight, and the BET specific surface area of the silica-magnesia gel is 526m ² /g, and the pore volume is 0.52ml/g.

Add 1800 grams of water in the reactor, add 48 grams of magnesium silica gel, 24 grams of lanthanum nitrate, 30 grams of aluminum sol, 180 grams of flake-shaped boehmite (prepared by the method provided in U.S. Patent 6403007, The specific surface area is 25.6m ² /g, the alumina content is 56.8% by weight, the thickness of the flakes is 10 nanometers, the addition is based on dry weight) and 318 grams of kaolin, after stirring for 30 minutes, it is spray-dried, and the temperature of the spray-dried tail gas is 140°C, then calcined at 500°C for 30 minutes to obtain catalytic cracking additive C.

The BET specific surface area of catalytic cracking aid C is 162m ² /g, the wear index is 1.0, and the heap ratio is 0.74g/ml.

Example 4

According to U.S. Patent No. 3,129,189, prepare fluorine-containing silica-magnesia gel. In the obtained silica-magnesia gel, the content of magnesium oxide is 28.0% by weight, and the content of silicon dioxide is 69.4% by weight based on the dry weight of silica-magnesia gel. % by weight, the content of sodium oxide is 0.1% by weight; the content of fluorine element is 2.5% by weight, the BET specific surface area of silica-magnesia gel is 526m ² /g, and the pore volume is 0.52ml/g.

Add 2000 grams of water into the reaction kettle, and then add 48 grams of silicon magnesium colloid, 27 grams of lanthanum oxide, and 18 grams of silica sol (provided by Fudan University, calculated as oxides, with a silicon dioxide content of 30.0% by weight, oxidized Sodium content 0.1% by weight, add-on is by weight on a dry basis), 270 grams of pseudo-boehmite and 237 grams of halloysite, spray drying after stirring for 30 minutes, the temperature of the spray drying tail gas is 120 ° C, then roasting at 650 ° C for 30 Minutes to obtain catalytic cracking additive D.

The BET specific surface area of catalytic cracking aid D is 158m ² /g, the wear index is 1.4, and the heap ratio is 0.72g/ml.

Example 5

According to U.S. Patent No. 3,129,189, prepare fluorine-containing silica-magnesia gel. In the obtained silica-magnesia gel, the content of magnesium oxide is 28.0% by weight, and the content of silicon dioxide is 69.4% by weight based on the dry weight of silica-magnesia gel. %, the content of sodium oxide is 0.1% by weight; the content of fluorine element is 2.5% by weight, and the BET specific surface area of the silica-magnesia gel is 526m ² /g, and the pore volume is 0.52ml/g.

Add 2000 grams of water to the reaction kettle, and then add 48 grams of silica-magnesia gel, 27 grams of samarium oxide, 18 grams of aluminum sol, 237 grams of pseudoboehmite and 270 grams of halloysite under vigorous stirring, and spray after stirring for 30 minutes Drying, spray drying tail gas temperature is 120°C, and then roasting at 550°C for 30 minutes to obtain catalytic cracking aid E.

The BET specific surface area of catalytic cracking aid E is 161 m ² /g, the wear index is 0.9, and the heap ratio is 0.74 g/ml.

Example 6

According to U.S. Patent No. 3,129,189, prepare fluorine-containing silica-magnesia gel. In the obtained silica-magnesia gel, the content of magnesium oxide is 28.0% by weight, and the content of silicon dioxide is 69.4% by weight based on the dry weight of silica-magnesia gel. % by weight, the content of sodium oxide is 0.1% by weight, the content of fluorine element is 2.5% by weight, and the BET specific surface area of the silica-magnesia gel is 526m ² /g, and the pore volume is 0.52ml/g.

Add 2000 grams of water to the reaction kettle, and then add 48 grams of silica-magnesia gel, 30 grams of cerium oxide, 18 grams of aluminum sol, 234 grams of pseudo-boehmite and 270 grams of halloysite under vigorous stirring, and spray after stirring for 30 minutes Drying, spray drying tail gas temperature is 120°C, and then roasting at 550°C for 30 minutes to obtain catalytic cracking aid F.

The BET specific surface area of catalytic cracking aid F is 156m ² /g, the wear index is 0.9, and the heap ratio is 0.76g/ml.

Example 7

According to U.S. Patent No. 3,129,189, prepare fluorine-containing silica-magnesia gel. In the obtained silica-magnesia gel, the content of magnesium oxide is 28.0 percent by weight, and the content of silicon dioxide is 69.4 percent by weight based on the dry weight of silica-magnesia gel. % by weight, the content of sodium oxide is 0.1% by weight; the content of fluorine element is 2.5% by weight, and the BET specific surface area of the silica-magnesia gel is 526m ² /g, and the pore volume is 0.52ml/g.

Add 2000 grams of water to the reaction kettle, and then add 48 grams of silicon-magnesium colloid, 27 grams of lanthanum oxide, and 30 grams of ZSM-5 (provided by Nankai University, the ratio of silicon to aluminum is 30, and the addition amount is calculated on a dry basis) under vigorous stirring. ), 18 grams of aluminum sol, 207 grams of pseudo-boehmite and 270 grams of halloysite, stirred for 30 minutes, spray-dried, and the temperature of the spray-dried tail gas was 120° C., and then roasted at 550° C. for 30 minutes to obtain catalytic cracking additive G .

The BET specific surface area of catalytic cracking aid G is 165m ² /g, the wear index is 1.2, and the heap ratio is 0.72g/ml.

Comparative example 1

The contrast agent was prepared according to the method of Example 1 in WO9712011.

Add 2159 grams of water to the reaction kettle, then add 270 grams of SASOL company SB powder, 71 grams of SASOL company Siral 5, 68 grams of formic acid, 833 grams of kaolin and 893 grams of gibbsite with a concentration of 28% by weight under vigorous stirring (produced by Shandong Aluminum Works, with an alumina content of 70% by weight) slurry, stirred for 30 minutes, spray-dried, spray-dried tail gas at a temperature of 145° C., and then roasted at 550° C. for 30 minutes to obtain contrast agent DB1.

The BET specific surface area of the contrast agent DB1 was 130 m ² /g, the wear index was 1.3, and the bulk ratio was 0.80 g/ml.

Comparative example 2

Contrast agent DB2 is an auxiliary agent Converter produced by BASF Company.

The BET specific surface area of the contrast agent DB2 is 430 m ² /g, the wear index is 1.6, and the bulk ratio is 0.73 g/ml.

The physical and chemical properties of the catalytic cracking additives prepared in the above examples and comparative examples are shown in Table 1.

Table 1

Example 8

This example illustrates the fixed fluidized bed evaluation results of the catalytic cracking additive provided by the present invention.

Through 800 ℃, 100% steam aging for 4 hours before the auxiliary agent evaluation, the auxiliary agent through hydrothermal aging and the balancing agent catalyzed by Sinopec Luoyang Branch (the balance agent micro-reaction activity is 65%, and the alumina content is 47.0% by weight , silicon oxide content 43.4% by weight, _RE2O3 content 3.8% by weight, phosphorus _pentoxide content 1.6% by weight, nickel oxide content 0.90% by weight, vanadium oxide content 0.82% by weight) by weight ratio 15: 85 mix homogeneously, raw material The oil is catalytic raw material oil produced by Sinopec Luoyang Branch Company, wherein the residual carbon content is 2.76 wt%, the density is 0.9068g/ml, and the sulfur content is 0.28 wt%. Evaluation conditions: the reaction temperature is 500°C, the weight space velocity is 30h ^-1 , and the agent-oil weight ratio is 6.0.

The catalytic cracking additives A-G prepared in Examples 1-7 and the contrast agents DB1 and DB2 were evaluated according to the above-mentioned method under the above-mentioned conditions, and the evaluation results are shown in Table 2. The blank sample in Table 2 is only catalytic balancer, without catalytic cracking additive.

Table 2

*The total liquid yield is the total yield of gasoline + diesel + liquefied petroleum gas

As can be seen from the fixed fluidized bed evaluation results given in Table 2, compared with the contrast agent, the catalytic cracking additives prepared in Examples 1-7 of the present invention can not only reduce the oil slurry yield, but also reduce the coke yield at the same time and dry gas yield.

Claims (10)

1. an assistant for calalytic cracking composition is characterized in that, in the gross weight of assistant for calalytic cracking composition; And in butt; This assistant for calalytic cracking composition contains the silicon magnesium glue of 2～65 heavy %, 1～25 heavy % rare earth compound, 15～85 heavy % one diaspores.

2. assistant for calalytic cracking composition according to claim 1 wherein, is a benchmark with the weight of silicon magnesium glue, and in oxide, magnesian content is 10～40 heavy % in the said silicon magnesium glue, is preferably 15～35 heavy %.

3. assistant for calalytic cracking composition according to claim 1 and 2, wherein, fluorine element content is 0.1～3 heavy % in the described silicon magnesium glue.

4. assistant for calalytic cracking composition according to claim 1, wherein, said rare earth compound is one or more in rare earth oxide, rare-earth hydroxide, rare earth nitrades and the rare earth carbonate.

5. assistant for calalytic cracking composition according to claim 1, wherein, a said diaspore is boehmite and/or boehmite.

6. assistant for calalytic cracking composition according to claim 5, wherein, being shaped as of said boehmite is laminar and/or fibrous.

7. assistant for calalytic cracking composition according to claim 1; Wherein, This assistant for calalytic cracking composition also contains the gross weight in the assistant for calalytic cracking composition, the clay of the MFI structure shape-selective molecular sieve of 0～5 heavy %, the binding agent of 2～10 heavy % and 0～60 heavy %.

8. assistant for calalytic cracking composition according to claim 7; Wherein, Gross weight in this assistant for calalytic cracking composition; And in butt; This assistant for calalytic cracking contains the silicon magnesium glue of 5～20 heavy %, the rare earth oxide of 1～10 heavy %, the diaspore of 15～65 heavy %, the MFI structure shape-selective molecular sieve of 0～5 heavy %, the binding agent of 2～10 heavy %, the clay of 20～60 heavy %, the clay of the binding agent of the diaspore of the silicon magnesium glue of preferred 8～15 heavy %, the rare earth oxide of 2～5 heavy %, 30～45 heavy %, the MFI structure shape-selective molecular sieve of 0～5 heavy %, 3～9 heavy % and 40～55 heavy %.

9. assistant for calalytic cracking composition according to claim 8; Wherein, Said clay is selected from one or more in kaolin, galapectite, sepiolite, diatomite, rectorite, attapulgite, bentonite and the imvite, and said binding agent is one or more in aluminium colloidal sol, Ludox, the Alusil.

10. an assistant for calalytic cracking is characterized in that, this assistant for calalytic cracking is by making through spray drying granulation and roasting after the making beating of any described assistant for calalytic cracking composition and water in the claim 1～9.